DIIMINE COMPLEXES OF RUTHENIUM(II), RHENIUM(I) AND IRON(II): FROM
SYNTHESIS TO DFT STUDIES
A Dissertation by
Robert Anthony Kirgan
B.S., Fort Hays State University, 2002
Submitted to the Department of Chemistry
and the faculty of the Graduate School of
Wichita State University
in partial fulfillment of
the requirements for the degree of
Doctor of Philosophy
August 2007
© Copyright 2007 by Robert Anthony Kirgan
All Rights Reserved
ii
DIIMINE COMPLEXES OF RUTHENIUM(II), RHENIUM(I) AND IRON(II): FROM
SYNTHESIS TO DFT STUDIES
I have examined the final copy of this dissertation for form and content, and recommend that it
be accepted in partial fulfillment of the requirement for the degree of Doctor of Philosophy with
a major in Chemistry.
_______________________________________
D. Paul Rillema, Committee Chair
We have read this dissertation and recommend its acceptance:
_______________________________________
Elizabeth Behrman, Committee Member
_______________________________________
Mel Zandler, Committee Member
_______________________________________
Francis D’Souza, Committee Member
_______________________________________
Ram Singhal, Committee Member
Accepted for the College of Liberal Arts and Sciences
______________________________
William D. Bischoff, Dean
Accepted for the Graduate School
______________________________
Susan Kovar, Dean
iii
DEDICATION
To my wife and son, Jessica and Kaleb
parents, John and Barb
brother and sister-in-law, Philip and Sarah
my extended family
and Dr. McGuirk and Shannon
iv
Eschew Obfuscation, Espouse Elucidation
Maxim of Manner
Paul Grice
v
ACKNOWLEDGEMENTS
I would like to thank Dr. D. Paul Rillema for all of his advice and support throughout the
years. He allowed me to explore new avenues and try new experiments that helped tremendously
in the development of my understanding and vastness of chemistry. I thank Dr. Melvin Zandler
and Dr. Francis D’Souza for their helpful discussions and teachings they gave me. I thank Dr.
Ram Singhal and Dr. Elizabeth Behrman for their suggestions and support. I thank Dr. Khamis
Siam for his helpful discussions and explanations in the execution of theoretical calculations.
I am grateful for all the students past and present in Dr. Rillema’s lab especially Dr.
Stoyanov. He helped me to understand and extend my knowledge of the application of
theoretical calculations to the understanding of experimental results. I also thank fellow graduate
students Amy and Curtis who were there as friends and collegues. I thank my wife for her
support, encouragement and shoulder to lean on. I thank my son, Kaleb, who spent the last year
of my college career giving me hope and encouragement in his own way. I thank my parents for
getting me to this point. I thank my immediate and extended family for their support. I also thank
Dr. McGuirk and nurse Shannon for giving me a second chance on life.
I thank the support of the Graduate Assitance for Areas of National Need for providing
the financial means of which I lived on. I thank the Wichita State University High Performance
Computing Center, Wichita State University Office of Research Administration, Department of
Energy, National Science Foundation, Wichita State University Department of Chemistry and
Parker Fellowship.
Finally I thank God for the abilities he has endowed in me and the family he gave me.
vi
ABSTRACT
The chloro and pyridinate derivatives of rhenium(I) tricarbonyl complexes containing the
diimine ligands 2,2’-bipyrazine (bpz) and 5,5’-dimethyl-2,2’-bipyrazine (Me2 bpz) are discussed.
When compared to similar rhenium(I) tricarbonyl complexes of 2,2’-bipyridine (bpy) and 2,2’bipyrimidine (bpm), the Me2bpz complexes are comparable to bpm derivatives and their
properties are intermediate between those of bpy and bpz complexes.
Also discussed is the synthesis and properties of two new analogues of ruthenium(II) trisbipyridine, a monomer and dimer. The complexes contain the ligand 6,6’-(1,2-ethanediyl)bis2,2’-bipyridine (O-bpy) which contains two bipyridine units bridged in the 6,6’ positions by an
ethylene group. Crystal structures of the two complexes formulated as [Ru(bpy)(O-bpy)](PF6)2
and [(Ru(bpy)2)2(O-bpy)](PF6)4 reveal structures of lower symmetry than D3 which affects the
electronic properties of the complexes as revealed by Density Functional Theory (DFT) and
Time Dependent Density Functional Theory (TDDFT) calculations.
Iron(II) tris-bipyrazine undergoes dissociation in solution with loss of the three
bipyrazine ligands. The rate of the reaction in acetonitrile depends on the concentration of
anions present in the solution. The rate is fastest in the presence of Cl- and slowest in the
presence of Br-. In a second discussion DFT calculations are used to explore four iron(II)
diimine complexes. DFT calculations show the higher energy HOMO (highest occupied
molecular orbital) orbitals of the four complexes are metal centered and the lower energy LUMO
(lowest unoccupied molecular orbitals) are ligand centered.
vii
TABLE OF CONTENTS
Chapter
Page
1. INTRODUCTION
1
1.1. The Many Aspects of Chemistry
1.2 Rhenium(I) Tricarbonyl complexes
1.3. Derivatives of Ruthenium(II) Tris-2,2’-Bipyridine
1.4. Solution and Physical Properties of Iron(II) Tris 2,2’-Bipyrazine
1.5. The use of DFT to understand experiment
2. RHENIUM COMPLEXES WITH TWO DERIVATIVES OF A
BIPYRAZINE LIGAND
2.1. Experimental
2.1.1. Materials
2.1.2. Synthesis
2.1.3. Computational Procedures
2.1.4. X-Ray Analysis
2.1.5. Physical Measurements
2.2. Results
2.2.1. Crystal Structures
2.2.2. Molecular Structures
2.2.3. Nuclear Magnetic Resonance Studies
2.2.4. Infrared Studies
2.2.5. Absorption Studies
2.2.6. Emission
2.2.7. Cyclic Voltammetry
2.3. Discussion
2.3.1. Calculated Structures
2.3.2. Molecular Orbitals
2.3.3. Molecular Orbital Energies
2.3.4. Absorption Studies
2.3.5. Infrared Vibrational Spectra
2.3.6. Nuclear Magnetic Resonance
2.3.7. Emission
2.3.8. Cyclic Voltammetry
2.4. Conclusion
viii
1
2
2
3
5
9
9
9
9
11
11
12
13
13
19
21
23
25
27
29
29
29
30
33
35
36
38
38
40
42
TABLE OF CONTENTS (continued)
3. COMPARISON OF THE PROPERTIES OF [Ru(2,2’-BIPYRIDINE)
(6,6’-(1,2-ETHANEDIYL)BIS-2,2’-BIPYRIDINE)]2+ AND
[(Ru(2,2’-BIPYRIDINE)2)2(6,6’-(1,2-ETHANEDIYL)
BIS-2,2’-BIPYRIDINE)]4+ TO [Ru(2,2’-BIPYRIDINE)3]2+
3.1. Experimental
3.1.1. Materials
3.1.2. Synthesis
3.1.3. Physical Measurements
3.1.4. Computational Procedures
3.1.5. X-Ray Analysis
3.2. Results
3.2.1. Crystal Structure
3.2.2. Absorption Studies
3.2.3. Electrochemistry
3.2.4. Excited State Studies
3.3. Discussion
3.3.1. Geometry Study
3.3.2. Molecular Orbitals
3.3.3. Absorption Studies
3.3.4. Emission Spectra
3.4. Conclusion
4. SOLUTION AND PHYSICAL PROPERTIES OF IRON(II)
TRIS 2,2’-BIPYRAZINE: KINETICS AND DFT CALCULATIONS
4.1. Experimental
4.2. Results
4.3. Kinetic Study
4.4. Conclusion
43
43
43
43
45
46
46
47
47
50
52
53
55
55
60
64
68
71
72
72
73
75
85
5. COMPUTATIONAL STUDY OF IRON(II) SYSTEMS CONTAINING
THE LIGANDS WITH NITROGEN HETEROCYCLIC GROUPS
5.1. Computational Technique
5.2. Geometry Optimization
5.3. Molecular Orbitals
86
86
88
89
ix
TABLE OF CONTENTS (continued)
5.4. Orbital Energy Levels
5.5. Discussion
5.5.1. Electrochemical Behavior
5.5.2. Energy Levels
5.5.3. Singlet Excited and UV-Vis Absorption Spectra
5.5.4. Comparison to Ru(II)
5.5.5. Chemical Behavior
5.6. Conclusion
6. CRYSTAL STRUCTURE REPORTS
92
94
94
96
97
101
102
103
104
6.1. fac-Bipyrazyltricarbonyl(aquo)Rhenium(I) Hexafluorophosphate
Dihydrate
6.1.1. Experimental
6.1.2. X-Ray Analysis and Refinement
6.1.3. Comment
6.2. 4b,5,7,7a-Tetrahydro-4b,7a-Epiminomethanoimino-6H-Imidazo
[4,5-f][1,10]Phenanthroline-6,13-dione Monohydrate
6.2.1. Experimental
6.2.2. X-Ray Analysis and Refinement
6.2.3. Comment
7. DETERMINATION OF QUANTUM YIELDS:
USE OF A STANDARD EQUATION
104
104
105
108
110
110
111
114
116
7.1. Introduction
7.2. Materials and Methods
7.3. Instrumentation
7.4. Experimental Procedure
7.5. Results and Discussion
7.6. Conclusion
116
117
117
117
120
125
8. CONCLUDING REMARKS
126
REFERENCES
128
x
TABLE OF CONTENTS (continued)
APPENDICES
141
A. Chapter 2 Supplementary Information
B. Chapter 3 Supplementary Information
C. Chapter 4 Supplementary Information
D. Chapter 5 Supplementary Information
E. Chapter 6 Supplementary Information
xi
142
222
271
281
341
LIST OF TABLES
Table
2.1
Crystallographic data and structure refinement
Page
16
2.2
Calculated vs. X-Ray bond distances (Å) and selected angles (◦)
20
2.3
NMR data with assignment of protons: Complex 1: Re(CO)3(bpz)Cl;
Complex 2: Re(CO)3(bpz)(py).PF6 ; Complex 3: Re(CO)3(Me2bpz)Cl;
Complex 4: Re(CO)3(Me2bpz)(py).PF6
22
2.4
Experimental, calculated, and scaled carbonyl stretch frequencies
(cm-1).
23
2.5
Absorption data and assignments (Values in parenthesis are extinction
coefficient)
25
2.6
Emission maxima obtained by excitation at the MLCT maxima and
excitation maxima obtained from excitation spectra.
27
2.7
Oxidation and Reduction potentials
29
2.8
Electron distribution within the rhenium(I) molecules and their Mulliken
charges
32
2.9
Experimental MLCT, calculated MLCT and scaled values.
35
2.10
Carbonyl stretch frequency comparison for 1 – 4 and similar compounds
37
2.11
Experimental, calculated and scaled emission energies
39
3.1
Crystal structure data collection information
49
3.2
Absorption data with extinction coefficients
50
3.3
Electrochemical data
52
3.4
Emission data
53
3.5
Bond distances (Å) and scheme showing bond locations
56
3.6
Angles (◦) describing the octahedral geometry around the ruthenium center
58
3.7
Dihedral angles (◦) for each of the ligands present on each molecule
60
xii
LIST OF TABLES (continued)
3.8
Table of percent contributions of each species for the LUMO+2 to the
HOMO-2 energy levels
63
3.9
Calculated emission data
68
4.1
Comparison of crystal structure to calculated bond distances and angles
73
4.2
Absorption band comparison [υ / 103 cm-1]
75
4.3
Rate constants and thermodynamic data
78
5.1
Experimental vs. Calculated Bond Distances (Å)
89
5.2
Detailed HOMO, LUMO, LUMO+1, LUMO+2 Electron Density
Distribution
91
5.3
Electrochemical Data and Mulliken Charges
96
5.4
Tabulated data for the experimental and calculated spectra
98
5.5
Calculated d-d Transitions (cm-1) and Absorption Coefficients (M-1cm-1)
100
6.1
Crystal Structure Data and Refinement
107
6.2
Rhenium-Oxygen and Oxygen-Oxygen bond distances (Å)
109
6.3
Crystal Structure Data and Refinement
113
6.4
Hydrogen bonds distances (Å) and angles (◦)
115
7.1
Quantum Yield Results
124
xiii
LIST OF FIGURES
Figure
1.1
Schematic drawings of [Ru(bpy)(O-bpy)]2+(left), [Ru(bpy)3]2+ (middle)
and [(Ru(bpy)2)2(O-bpy)]4+ (right)
Page
3
1.2
Illustration of the different types of stretches observed for the carbonyl
groups attached to rhenium in rhenium tricarbonyl complexes
6
1.3
Exerpt of the transitional results obtained from a TDDFT calculation
output
7
2.1
Schematic drawing of complexes: (1) Re(CO)3(bpz)Cl, (2)
Re(CO)3(bpz)(py).PF6, (3) Re(CO)3(Me2bpz)Cl, (4)
Re(CO)3(Me2bpz)(py).PF6
14
2.2
ORTEP figures with thermal ellipsoids drawn at the 50% probability
level.183; Complex 1: Re(CO)3(bpz)Cl; Complex 2: Re(CO)3(bpz)(py).PF6 ;
Complex 3: Re(CO)3(Me2bpz)Cl; Complex 4: Re(CO)3(Me2bpz)(py).PF6
15
2.3
Crystal packing for [Re(CO)3(Me2bpz)(py).PF6] as seen down the 001 face
18
2.4
IR spectra of the carbonyl stretch region: (1) Re(CO)3(bpz)Cl, (2)
Re(CO)3(bpz)(py).PF6, (3) Re(CO)3(Me2bpz)Cl, (4)
Re(CO)3(Me2bpz)(py).PF6
24
2.5
Experimental spectra (__) and scaled calculated spectra (---) in acetonitrile
where (1) Re(CO)3(bpz)Cl, (2) Re(CO)3(bpz)(py).PF6, (3)
Re(CO)3(Me2bpz)Cl, (4) Re(CO)3(Me2bpz)(py).PF6
26
2.6
Emission spectra at 77 K excited at the MLCT maxima where (1)
Re(CO)3(bpz)Cl, (2) Re(CO)3(bpz)(py).PF6, (3) Re(CO)3(Me2bpz)Cl, (4)
Re(CO)3(Me2bpz)(py).PF6
28
2.7
Graphical representation of optimized structure, HOMO orbital, LUMO
orbital where (1) Re(CO)3(bpz)Cl, (2) Re(CO)3(bpz)(py).PF6, (3)
Re(CO)3(Me2bpz)Cl, (4) Re(CO)3(Me2bpz)(py).PF6
31
2.8
Molecular orbital energy diagram for nine frontier occupied orbitals and
nine frontier virtual orbitals of (1) Re(CO)3(bpz)Cl, (2)
Re(CO)3(bpz)(py).PF6, (3) Re(CO)3(Me2bpz)Cl, (4)
Re(CO)3(Me2bpz)(py).PF6 in the singlet ground state in the gas phase. A =
Re/CO/Cl, B = Re/CO, C = Re/Cl, L = Ligand, Py = Pyridine
34
xiv
LIST OF FIGURES (continued)
2.9
Calculated Triplet Excited States Relative to Ground States of (1)
Re(CO)3(bpz)Cl, (2) Re(CO)3(bpz)(py).PF6, (3) Re(CO)3(Me2bpz)Cl, (4)
Re(CO)3(Me2bpz)(py).PF6
39
2.10
Correlation charts of HOMO vs. 1st Oxidation and LUMO vs. 1st
Reduction. Left: Chloride containing compounds: bpy-[Re(CO)3(bpy)Cl],
bpm-[Re(CO)3(bpm)Cl] bpz-[Re(CO)3(bpz)Cl] Me2bpz[Re(CO)3(Me2bpz)Cl]; Right: Pyridine containing compounds: bpy{[Re(CO)3(bpy)(py)]+}, bpm-{[Re(CO)3(bpm)(py)]+}, bpz{[Re(CO)3(bpz)(py)]+}, Me2bpz-{[Re(CO)3(Me2bpz)(py)]+}.
41
3.1
Crystal structure of [Ru(bpy)(O-bpy)]2+ and [(Ru(bpy)2)2(O-bpy)]4+ (50%
ellipsoids)
48
3.2
Experimental spectra for [Ru(bpy)3]2+ (black line), [Ru(bpy)(O-bpy)]2+
(blue line), [(Ru(bpy)2)2(O-bpy)]4+ (red line).
52
3.3
Emission spectra at 77K for [Ru(bpy)(O-bpy)]2+ (blue), [(Ru(bpy)2)2(Obpy)]4+ (red) both normalized to [Ru(bpy)3]2+ (black)
54
3.4
Schematic drawing of the molecules with letters corresponding to the
angles in Table 3.5
58
3.5
Schematic drawing of the bond angles
59
3.6
Scheme showing the two rings systems and the atoms selected to measure
the dihedral angle
60
3.7
HOMO and LUMO orbital diagrams
62
3.8
Graphical representation of the orbital contributions: Red – Ruthenium
orbitals, Green – O-bpy, Blue – bpy. The order of the columns in each set
of three is [Ru(bpy)3]2+, [Ru(bpy)(O-bpy)]2+, [(Ru(bpy)2)2(O-bpy)]4+
63
3.9
Simulated (----, gas phase) and experimental (―, acetonitrile) absorption
spectra for [Ru(bpy)(O-bpy)]2+
65
3.10
Frontier orbital energy diagram for the six occupied (HOMO to HOMO-5)
and six virtual orbitals (LUMO to LUMO+5).
67
3.11
Diagram showing the calculated emission energy in relation to the
experimental energy
70
xv
LIST OF FIGURES (continued)
4.1
Absorption spectrum of Fe(bpz)32+ in acetonitrile
74
4.2
Series of absorption data taken for the reaction of Fe(bpz) 32+ with water ,
the red line shows the absorption after 3 minutes. (Insert: Expanded region
from 200 to 325 nm, blue circles indicate isosbestic points.)
76
4.3
Graphs obtained from the reaction of Fe(bpz) 32+with chloride ion over 1
second, each trace represents 0.125 seconds
77
4.4
Expanded 3-dimensional view of the data shown in Figure 4.3
78
4.5
Decay curves for the three analytes when reacted with Fe(bpz) 32+ in
acetonitrile
79
4.6
kobs vs. anion concentration for the reaction of Fe(bpz) 32+ with chloride
80
4.7
Purposed mechanism for the reaction of Fe(bpz)32+ with an anion
82
4.8
DFT calculated mechanism for the reaction of Fe(bpz) 32+ with an anion
84
5.1
Schematic drawing of complexes; 1: Fe(bpy)32+; 2: Fe(bpz)32+; 3:
Fe(phen)32+; 4: Fe(tpy)22+
87
5.2
Molecular orbital diagrams for the optimized structure, HOMO and
LUMO orbitals; 1: Fe(bpy)32+; 2: Fe(bpz)32+; 3: Fe(phen)32+; 4: Fe(tpy)22+
90
5.3
Six occupied and six virtual frontier orbitals; 1: Fe(bpy) 32+; 2: Fe(bpz)32+;
3: Fe(phen)32+; 4: Fe(tpy)22+
93
5.4
Left: Plot of HOMO energy vs. oxidation potential, Right: Plot of LUMO
energy vs. 1st reduction potential; 1: Fe(bpy)32+; 2: Fe(bpz)32+; 3:
Fe(phen)32+; 4: Fe(tpy)22+
95
5.5
Singlet excited state spectra with transitions shown as vertical bars; Top
left: Fe(bpy)32+; top right: Fe(bpz)32+; bottom left: Fe(phen)32+; bottom
right: Fe(tpy)22+
99
6.1
Schematic drawing of Re(CO)3(bpz)(H2O).PF6.2H2O
105
6.2
ORTEP drawing with 50% probability
108
xvi
LIST OF FIGURES (continued)
6.3
Schematic drawing of 4b,5,7,7a-tetrahydro-4b,7a-epiminomethanoimino6H-imidazo[4,5-f][1,10]phenanthroline-6,13-dione monohydrate
111
6.4
ORTEP drawing with 50% probability
114
7.1
Schematic of Room Temperature Degassing Cell
119
7.2
Plot of selected values; 1: Ru(bpy)32+ in 4:1 EtOH:MeOH at 298K; 2:
Ru(bpy)32+ in propylene carbonate at 298K; 3: Ru(bpy)2(CN)2 in 4:1
EtOH:MeOH at 77K; 4: Ru(bpy)32+ in 4:1 EtOH:MeOH at 77K;
Rhodamine B in EtOH at 298K; Rhodamine 6G in water at 298K
122
xvii
LIST OF ABBREVIATIONS / NOMENCLATURE
A
Absorbance
B3LYP
Becke’s 3 parameter hybrid functional with non-local correlation
functional of Lee, Yang and Parr
bpm
2,2’-bipyrimidine
bpy
2,2’-bipyridine
bpz
2,2’-bipyrazine
CH3CN
Acetonitrile
CO
Carbonyl
CPCM
Conductor-like Polarizable Continuum Model
CT
Charge Transfer
dafo
4,5-diazafluren-9-one
DFT
Density Functional Theory
DMF
Dimethyl Formamide
EtOH
Ethanol
f
Oscillator Strength
fwmh
Full Width at Middle Height
GS
Ground State
HOMO
Highest Occupied Molecular Orbital
I
Intensity
IR
Infra-Red
LC
Ligand Centered
LUMO
Lowest Unoccupied Molecular Orbital
xviii
LIST OF ABBREVIATIONS / NOMENCLATURE (continued)
MC
Metal Centered
Me2bpz
5,5’-dimethyl-2,2’-bipyrazine
MeOH
Methanol
MLCT
Metal-to-Ligand Charge Transfer
MLLCT
MetalLigand-to-Ligand Charge Transfer
NMR
Nuclear Magnetic Resonance
O-Bpy
6,6’-(1,2-ethanediyl)bis-2,2’-bipyridine
phen
1,10-phenanthroline
py
Pyridine
SDD
Stuttgart/Dresden ECPs
TBABF4
Tetrabutyl ammonium tetrafluoroborate
TBABr
Tetrabutylammonium bromide
TBAClO4
Tetrabutylammonium perchlorate
TBAH
Tetrabutylammonium hexafluorophosphate
TBASCN
Tetrabutylammonium thiocyanate
TDDFT
Time-Dependent Density Functional Theory
TEACl
Tetraethylammonium chloride
TMS
Tetramethylsilane
UV-Vis
Ultra-Violet and Visible
ε
Molar Absorptivity Coefficient
η
Refractive Index
κR
Correction Factor
xix
LIST OF ABBREVIATIONS / NOMENCLATURE (continued)
λem
Emission Wavelength
λex
Excitation Wavelength
τ
Lifetime
Φ
Quantum Yield
∆G‡
Activation Free Energy
∆H‡
Activation Enthalpy
∆S‡
Activation Entropy
xx
CHAPTER 1
INTRODUCTION
1.1. The many aspects of chemistry
The term chemistry is broad term that covers many different ideas and topics. The
definition given is a science that deals with the composition, structure, and properties of
substances and of the transformations that they undergo. Within this area there are many
specializations which are broken down to even more specialized fields. The research that will be
presented in this thesis covers many of these regions and shows how they all can overlap and
interact. The study of inorganic chemistry has evolved over the years to incorporate more
organic chemistry and other disciplines. This has allowed for the gap between the divisions to be
bridged and new exciting complexes to be created. These complexes have been useful for solar
energy and conversion1-26, and biochemical applications27-45.
The main focus of this thesis is the application of many different techniques to make
interesting and useful complexes that can be studied by photochemical means. Many of the
complexes absorb in the visible region (350 – 650 nm) with very strong absorptions in the UV
region (150 – 350 nm). The excitation of these bands can cause emission to occur. Ruthenium(II)
complexes have very nice emission in the 550 to 750 nm region whereas rhenium(I) complexes
show emission bands at 450 to 650 nm. The emission bands are assigned to triplet metal to
ligand charge transfer (3MLCT) transitions46. The assignments are made by spectroscopic
observations and TDDFT calculated assignments agree with experiment. Excited states, emission
spectra and lifetimes will be discussed in the various chapters.
1
1.2. Rhenium(I) tricarbonyl complexes
A
number
of
different
Re(diimine)(CO) 3Cl,
[Re(diimine)(CO)3(py)]+
and
[Re(diimine)(CO)3(py-X)]+, where X is a substituent bonded to py, complexes have been
synthesized. Some have been studied for their photophysical properties 47-68, others for solar
energy conversion49,69-73 and others for potential applications based on their emission
characteristics74-76.
In some cases, emission from Re(I) tricarbonyl diimine complexes occurs at high energy
(500-600 nm) with structure; in others it occurs at lower energy (600-700 nm) with broad,
structureless bands that are sensitive to their environment 47,48,50-53,66. Further, changing the
ancillary ligand from chloride to pyridine enhances the emission properties by increasing the
emission lifetimes and emission quantum yields of the excited states. Changes in the electronic
characteristics of the diimine ligand also affect the emission properties 77 which will be examined
in chapter 2 by way of comparing experimental to theoretical results.
The chloro and pyridinate complexes of rhenium tricarbonyl 2,2’-bipyrazine and 5,5’dimethyl-2,2’-bipyrazine are investigated in chapter 2.
The chloride containing bipyrazine
complex was synthesized and studied before64,78-80, but not in great detail.
The synthesis,
photochemistry, crystal structures, and computational studies are presented here for all four
complexes. All of these complexes have facial carbonyl groups and are luminescent at 77 K.
They will be divided into two subgroups, chloride bound, and pyridine bound and compared to
analogues in the literature.
1.3. Derivatives of Ruthenium(II) Tris-2,2’-Bipyrdine
Numerous studies related to ruthenium(II) tris-2,2’-bipyridine have been published ever
since the discovery of electron transfer from its excited state81-95. A large number of diimine
2
derivatives have been reported with the goal of enhancing the photophysics of excited state
electron or energy transfer for application to chemical systems. Changes in the structure of the
diimine ligands by addition of various functional groups have given rise to applications such as
intercalation into DNA96-124, solar electrochemical cells1-26, and biosensors27-45.
In chapter 3 the examination of how the physical and photophysical properties of
ruthenium tris- bipyridine are altered by the simple addition of an ethyl bridge located in the 6
position between two bipyridine rings as shown in Figure 1.1. The crystal structures, absorption
data, photophysical data, electrochemical information and DFT and TDDFT studies for
[Ru(bpy)(O-bpy)]2+, [(Ru(bpy)2)2(O-bpy)]4+ and [Ru(bpy)3]2+, where O-bpy is 6,6‖-(1,2ethanediyl)bis-2,2’-bipyridine and bpy is 2,2’-bipryridine, are compared.
2+
2+
N
4+
N
N
N
N
N
N
N
N
N
N
N
Ru
Ru
Ru
N
N
N
N
N
C
H2
H2C
Ru
N
N
N
CH 2
N
N
N
N
CH 2
Figure 1.1. Schematic drawings of [Ru(bpy)(O-bpy)]2+(left), [Ru(bpy)3]2+ (middle) and
[(Ru(bpy)2)2(O-bpy)]4+ (right)
1.4. Solution and Physical Properties of Iron(II) Tris 2,2’-Bipyrazine
Dissociation reactions of iron(II) tris-diimine complexes125-145 in aqueous solution have
been studied in the past.125-136,139,145 The reactions were studied in the presence of acid, base and
cyanide ions.127-129,131,134,135,138,144 Other aspects of the reaction such as the nature of the counter
ions and medium have also been considered.125,126,130,132,133,136 The postulated mechanism for the
dissociation of Fe(bpy)32+ and Fe(phen)32+ in acid solution involves breaking of the iron nitrogen
3
bond as the slow step which allows for protonation leading to loss of the coordinated ligand by
substitution of both species.131,145
The dissociation kinetics of Fe(bpz)32+ were also reported by Gillard et al. 138 who
postulated that the reaction involved attack on the bipyrazine ring leading to rupture of the C-C
bond between the pyrazine rings of the bipyrazine ligand. The breakage of a bond would be a
high energy process leading to the presence of free radicals in solution. This mechanism seems
unusual, especially in light of the rapid dissociation of the complex in water.
In chapter 4 examination of the reactivity of Fe(bpz)32+ with three anions in acetonitrile
and propose a mechanism which is reinforced with DFT calculations outlining the likely reaction
pathway. Anion substitution is shown to play a significant role in the dissociation process. This
approach provides new insight into the mechanism of these dissociation reactions.
Iron(II) diimine complexes show similar electronic and chemical properties. 137-143,146
Compared to its congener, ruthenium(II) which has the same d 6 electronic configuration, the
iron(II) analogues are less stable and undergo ligand loss more readily. When diimine ligands,
such as bipyridine, are bound to ruthenium the molecule is very stable under most conditions, but
when bound to iron a decomposition reaction occurs. Ligand loss occurs very rapidly in some
cases such as in Fe(bpz)32+. In others, such as in Fe(bpy)32+, it occurs more slowly.
In an attempt to understand the variation in the properties between iron(II) and
ruthenium(II) and the differences in stability between iron(II) diimine complexes, chapter 5
contains a general computational study on four iron(II) complexes used to ascertain these
differences. We147,148 and others149,150 have examined ruthenium(II) complexes in the past; here
we focus on three iron (II) diimine systems, 2,2’-bipyridine, 2,2’-bipyrazine, and 1,10-
4
phenanthroline
125-136
, and one iron (II) triimine, Fe(terpy) 22+, where terpy is 2,2’:6’,2’’-
terpyridine.
1.5. The use of DFT to understand experiment
As stated previously DFT is a very efficient and functional tool in the understanding of
the experimental results. One must be careful when trying to compare results not to take the
calculated data as fact. There can be many flaws with the procedure which was used to perform
the calculations. If careful attention is given to the set up and processing of the data then the
results can be a very powerful tool.
The simplest way the data can be used is to compare bond distances and over all
molecular shape. If the data are compared to crystal structure data, the bond distances will be
longer and angles will be slightly different. This is mainly due to the packing effects and forces
induced by the other molecules within the crystal lattice. It is observed that the same trends in
bond lengths can be seen in calculated structures. In other words the shortest bond distance in the
crystal will most likely be the shortest bond in the calculated structure. If any of these distances
are extremely different from the crystal structure one must look at the quality of the structure
calculated.
The optimized structure’s wave function can be used to calculate many different
properties of the molecule. When the second derivative of the wave function is calculated,
properties such as NMR, IR, ESR and CD spectra can be determined. When the IR spectra of
rhenium tricarbonyl complexes were calculated, the identity of the three stretches observed
experimentally could be assigned, Figure 1.2. The calculations showed that the two low energy
bands resulted from two different types of stretches. They can switch order, but they are always
the lowest in energy. The high energy stretch results from an asymmetric stretch that has the
5
equatorial carbonyl group moving opposite the two axial carbonyl groups. This is useful
reference information and can assist in the determination of structure during transient spectral
experiments. The carbonyl region gives a very nice handle to observe the oxidation of the metal,
reductions of ligands and substitution.
Asymmetric
Symmetric
Highest energy stretch
Asymmetric
Lower energy stretches
Figure 1.2. Illustration of the different types of stretches observed for the carbonyl groups
attached to rhenium in rhenium tricarbonyl complexes
The most recent method developed is TDDFT (Time Dependent Density Functional
Theory). The wave function is perturbed and then the relaxation of the wave function to the
ground state yields transitional energies. These energies can be interpreted as absorption or
emission spectra. Each transition arises from the change between two different orbitals and
assignments can be made using these orbitals. In general each of the transitions calculated will
yield multiple sets of orbitals that are responsible for that transition at that energy. One statement
that needs to be made is that difference in energy calculated between two electronic energies is
not the same as the calculated transitional energies between the same electronic states. The
HOMO-LUMO gap is usually involved in the lowest energy transition but it is not always the
major transition that makes up the MLCT.
6
When the output file is obtained the transitions are printed as seen in Figure 1.3. Starting
from left and going right the items printed are the excited state number, spin state and symmetry,
transition energy in eV, transition position in nanometers and the oscillator strength, f, of the
transition.
On the next line are the orbitals that make up the transition starting with the commencing
orbital and ending with the destination orbital. The last number on the line is the contribution of
that transition to the overall transition. The percent contribution can be obtained by dividing the
square of the contribution by the sum of the squares of all contributions, shown in parathensis.
The number in parenthesis is the result. In Figure 1.3 there are two major components of the
transition the 128 to 133 and 129 to 132, each contributing 40%. The other two transitions only
contribute a total of 20% so they are considered not as important. After the major component(s)
is/are determined then the makeup of the individual orbitals is determined. These designations
are then used to assign the transition an identity. For example in Figure 1.3 orbital 128 is metal
centered and orbital 131 is ligand centered so the transition is assigned as a MLCT. In all four
parts of the transition seen in Figure 1.3 the assignment is MLCT, so the overall transition is a
MLCT. There are more complex cases where the transitions are mixed, and in those cases the
major components are considered. There can be transitions in which the assignment is a
combination of a d-d and MLCT or an ILCT and MLCT.
Excited State 7: Singlet-?Sym 2.9290 eV 423.30 nm f=0.1056
128 ->131
-0.19962
(8%)
128 ->133
0.42710
(40%)
129 ->131
-0.23297
(12%)
129 ->132
-0.42392
(40%)
Figure 1.3. Exerpt of the transitional results obtained from a TDDFT calculation output
7
Once the transitions are determined it is necessary to convert oscillator strengths (f) to
extinction coefficients (εmax). Equation 1.1 allows for the conversion by using an experimental
full width at middle height (fwmh). The trick to the equation is picking an accurate fwmh. In
this work, a fwmh of 3000 cm-1 was used for each transition. There is also a general cutoff for
the oscillator strength of 0.001, but this is not always the case when one wants to look for buried
transitions, such as d-d transitions.
f = 4.32x10-9 εmax ∆ω1/2
(1.1)
The program GaussSum has been used throughout the thesis to process the TDDFT
spectra. This program generates spectra and all of the transitions with a breakdown of the
different orbitals involved. This has cut the time by a factor of 1000 in processing a TDDFT
spectrum. The accuracy of the program has been checked by manually calculating an overall
spectrum and comparing it to the spectrum generated. The results showed nice agreement
between the two, so the program was used.
8
CHAPTER 2
RHENIUM COMPLEXES WITH TWO DERIVATIVES OF A BIPYRAZINE LIGAND
2.1. Experimental Section
2.1.1. Materials
The ligands 2,2’-bipyrazine151 (bpz) and 5,5’-dimethyl-2,2’-bipyrazine152 (Me2bpz) were
prepared as previously reported.
Re(CO)5Cl was purchased from Aldrich.
Optima grade
methanol was purchased from Fischer Scientific, while dry acetonitrile was purchased from
Sigma-Aldrich.
AAPER Alcohol and Chemical Co. was the source of absolute ethanol.
Tetrabutylammonium perchlorate was purchased from Southwestern Analytical Chemicals, Inc.
and dried in a vacuum oven before use. Ethanol and methanol were used in a 4:1 (v/v) mixture
to prepare solutions for the emission spectral and lifetime studies. Elemental analyses were
obtained from M-H-W Laboratories, Phoenix, AZ.
2.1.2. Synthesis
Re(bpz)(CO)3Cl (1): Re(CO)5Cl (0.10 g, 2.77 mmol) and bpz (0.044 g, 2.77 mmol) were mixed
in a one to one ratio in 20 mL of ethanol. The mixture was refluxed for 3 hours and allowed to
cool. The mixture was slowly evaporated to yield crystals suitable for x-ray structure analysis.
(Yield = 95%). Anal. Calcd for ReC11H6N4O3Cl: C, 28.48; H, 1.30; N, 12.08; Found: C, 28.55;
H, 1.50; N, 11.87.
[Re(bpz)(CO)3py]PF6 (2): Re(CO)5Cl (0.10 g, 2.77 mmol) and Ag(CF3SO3) (0.071 g, 2.77
mmol) were refluxed together in 20 mL of ethanol overnight. The AgCl that formed was
removed by filtration and bpz (0.044 g, 2.77 mmol) was added to the filtrate. The filtrate was
9
heated to reflux and then pyridine (0.022 g, 2.80 mmol) was added to the mixture. This solution
was refluxed for 4 hours. The volume of the solvent was then reduced to 5 mL. The mixture
was added into a magnetically stirred, saturated aqueous solution of ammonium
hexafluorophosphate. The solid that formed was filtered and dried. (Yield = 80%). Suitable
crystals for x-ray structure analysis were obtained from slow dissolution of an ethanol solution
into water. The crystals were grown in the dark to prevent photosubstitution of water. Anal.
Calcd for ReC16H11N5O3PF6: C, 29.45; H, 1.70; N, 10.73; Found: C, 28.71; H, 1.50; N, 10.71.
Re(Me2bpz)(CO)3Cl (3): The same procedure for the preparation of 1 was followed except that
5,5’-dimethyl-2,2’-bipyrazine (0.052 g, 2.77 mmol) was used in the place of 2,2’-bipyrazine.
Upon slow evaporation of the reaction mixture, crystals suitable for x-ray structure analysis were
obtained. (Yield = 95%) Anal. Calcd for ReC13H10N4O3Cl: C, 31.74; H, 2.05; N, 11.39; Found:
C, 31.93; H, 1.97; N, 11.32.
[Re(Me2bpz)(CO)3py]PF6 (4): The same procedure for the preparation of 2 was followed except
5,5’-dimethyl-2,2’-bipyrazine (0.052 g, 2.77 mmol) was used in the place of 2,2’-bipyrazine.
(Yield = 80%) Anal. Calcd for ReC18H15N5O3PF6: C, 31.77; H, 2.22; N, 10.29; Found: C, 31.67;
H, 2.07; N, 10.20.
10
2.1.3. Computational Procedures
Calculations were effected using Gaussian ’03 (Rev. B.03)153 for UNIX. The molecules
were optimized using Becke's three-parameter hybrid functional B3LYP154 with the nonlocal
term of Lee, Yang, and Parr and the local term of Vosko, Wilk, and Nassiar. The basis set
SDD155 was chosen for all atoms and the geometry optimizations were all run in the gas phase.
Nonequilbrium TDDFT156/CPCM157 calculations were employed to produce a number of singlet
excited states158 in acetonitrile based on the optimized geometry in the gas phase.
The
calculation is nonequilbrium with respect to the polarization of the solvent reaction field and the
electronic state of the input. For singlet excited states, this is the singlet ground state 159a. All
oscillator values and singlet and triplet excited state values are presented in the supporting
information found in the APPENDIX A. The simulated absorption spectra were run in the
solvent acetonitrile to match experimental conditions. All vibrational analyses revealed no
negative frequencies and were run in the gas phase only.
2.1.4. X-Ray Analysis
The crystal was affixed to a nylon cryoloop using oil (Paratone-n, Exxon) and mounted in
the cold stream of a Bruker Kappa-Apex-II area-detector diffractometer160. The temperature at
the crystal was maintained at 150 K using a Cryostream 700EX Cooler (Oxford Cryosystems).
The unit cell was determined from the setting angles of 218 reflections collected in 36 frames of
data. Data were measured with a redundancy of 6.2 using a CCD detector at a distance of 50
mm from the crystal with a combination of phi and omega scans. A scan width of 0.5 degrees
and a time of 10 seconds were employed along with graphite mono-chromated molybdenum Kα
radiation (λ= 0.71073 Å) that was collimated to a 0.6 mm diameter. Data collection, reduction,
structure solution, and refinement were performed using the Bruker Apex2 suite (v2.0-2) 160 . All
11
available reflections to 2θmax = 52° were harvested and corrected for Lorentz and polarization
factors with Bruker SAINT (v6.45)160. Reflections were then corrected for absorption, interframe
scaling, and other systematic errors with SADABS 2004/1. The structure was solved (direct
methods) and refined (full-matrix least-squares against F2) with the Bruker SHELXTL package
(v6.14-1)160. All non-hydrogen atoms were refined using anisotropic thermal parameters. All
hydrogen atoms were included at idealized positions and not refined.
2.1.5. Physical Measurements
Absorption
measurements
were
determined
with
a
HP8452A
Diode
Array
spectrophotometer and data was acquired with OLIS Global works software. All extinction
coefficients were determined in acetonitrile from Beer’s Law. Fluorescence measurements were
obtained with a Spex Fluorolog 2:1:2 spectrophotometer. The solvent for both room temperature
and 77 K studies was a fresh solution of 4:1 ethanol/methanol. All samples were degassed using
the freeze-pump-thaw method three or four times; residual gas had a pressure of ~ 150 mTorr.
The absorbance was set to 0.1 at the λ max for complex 1 – 3 and at 374 nm for complex 4. All
NMR spectra were obtained on a Varian 400 MHz spectrometer. The solvent was DMSO with
TMS as an internal standard. A Nicolet Avatar 360 FTIR was utilized to gather IR data. The
samples were pressed into a KBr pellet and ran with an instrument resolution of 4 cm -1.
Cyclic voltammograms were obtained in acetonitrile with 0.1 M tetrabutylammonium
perchlorate (TBAClO4) as the supporting electrolyte. A platinum metal disk was used for the
working electrode and a platinum wire functioned as the auxiliary electrode.
All
voltammograms were recorded versus a Ag/AgCl electrode. A PAR EG&G (Model 263A)
Potentiostat/Galvanostat was used to obtain the data and the PAR data interpreting program was
used to process the data.
12
2.2. Results
2.2.1. Crystal Structures
Crystallographic data and structure refinement data for complexes 1 - 4 are listed in Table
2.1, schematic drawings are shown in Figure 2.1 and ORTEP diagrams are shown in Figure 2.2.
The bpz containing complexes crystallized in the P-1 space group, whereas the Me2bpz
containing complexes packed in the R-3 space group (Table 2.1). It is unclear why such a simple
change in the ligand caused the difference in the crystal space groups for these complexes. As
shown in the packing diagram in Figure 2.3 for 4, six molecules form a six cornered ―star‖ with
an acetonitrile molecule in the center in the R-3 space group. There are three molecules on top
and three on bottom, and they alternate around the ―star.‖ The carbonyl groups make up the
inner part and the PF6- anions are tucked into the pocket between each cation.
13
O
N
O
N
O
O
N
N
F
F
Re
Re
F
Cl
N
F
O
N
O
P
F
N
F
N
N
2
1
O
N
O
N
O
O
N
F
N
Re
F
F
P
F
Re
N
Cl
O
N
O
F
F
N
N
N
4
3
Figure 2.1. Schematic drawing of complexes: (1) Re(CO)3(bpz)Cl, (2) Re(CO)3(bpz)(py).PF6,
(3) Re(CO)3(Me2bpz)Cl, (4) Re(CO)3(Me2bpz)(py).PF6
14
Figure 2.2. ORTEP figures with thermal ellipsoids drawn at the 50% probability level. 183;
Complex 1: Re(CO)3(bpz)Cl; Complex 2: Re(CO)3(bpz)(py).PF6;
Complex 3: Re(CO)3(Me2bpz)Cl; Complex 4: Re(CO)3(Me2bpz)(py).PF6
15
Table 2.1. Crystallographic data and structure refinement
1: Re(CO)3(bpz)Cl
Empirical formula
C11H6N4O3Cl1Re
Formula weight
Temperature
Wavelength
Crystal system
Space group
Unit cell dimensions
463.85
150 K
0.71073 Å
Triclinic
P-1
a = 6.4993(4) Å
b = 6.5962(4) Å
c = 15.2702(8) Å
α = 101.790(2)°
β = 92.935(3)°
γ = 102.198(2)°
623.31(6) Å3
2
2.471g/cm3
9.974 mm-1
432
0.51 x 0.16 x 0.08 mm
Needle
Lustrous Dark Red
16
Complex
Volume
Z
Calculated density
Absorption coefficient
F(000)
Crystal size
Crystal habit
Crystal color
2: Re(CO)3(bpz)(py).PF6
C16H11N5O3 PF6Re
· ½ H2 O
661.47
150 K
0.71073 Å
Triclinic
P-1
a = 8.3921(3) Å
b = 8.5622(3) Å
c = 14.5139(6) Å
α = 90.727(2)°
β = 104.250(2)°
γ = 95.379(2)°
1005.66(7) Å3
2
2.181 g/cm3
6.209 mm-1
628
0.30 x 0.20 x 0.10 mm
Prism
Clear Light Red
16
3: Re(CO)3(Me2bpz)Cl
C13H10N4O3Cl2Re
491.90
150 K
0.71073 Å
Rhombohedral
R-3
a = 27.1050(5) Å
b = 27.1050(5) Å
c = 11.2195(4) Å
α = 90 °
β = 90°
γ = 120°
7138.4(3) Å3
18
2.060 g/cm3
7.844 mm-1
4176
0.21 x 0.16 x 0.14 mm
Prism
Clear Intense Orange
4: Re(CO)3(Me2bpz)(py).PF6
C18H15N5O3PF6Re
·CH3CN
680.52
150 K
0.71073 Å
Rhombohedral
R-3
a = 33.2103(3) Å
b = 33.2103(3) Å
c = 10.6556(2) Å
α = 90 °
β = 90°
γ = 120°
10177.8(2) Å3
18
2.017 g/cm3
5.525 mm-1
5926
0.12 x 0.12 x 0.08 mm
Needle
Clear Intense Orange
Table 2.1. continued
4: Re(CO)3(Me2bpz)(py).PF6
3.22 to 26.00o
1.45 to 25.99o
-8 ≤ h ≤ 7
-10 ≤ h ≤ 10
-8 ≤ k ≤ 8
-10 ≤ k ≤ 10
-18 ≤ l ≤ 18
-17 ≤ l ≤ 17
17236 / 2430
17584 / 3959
[R(int) = 0.0265]
[R(int) = 0.0215]
99.9 %
99.9 %
Full-matrix least-squares on F2
3.62 to 25.99o
-33 ≤ h ≤ 32
-33 ≤ k ≤ 33
-13 ≤ l ≤ 13
38984 / 3070
[R(int) = 0.0604]
98.4 %
3.19 to 25.99o
-40 ≤ h ≤ 40
-40 ≤ k ≤ 40
-12 ≤ l ≤ 13
93689 / 4407
[R(int) = 0.0874]
99.3 %
2430 / 0 / 181
3959 / 0 / 298
3070 / 0 / 201
4407 / 2 / 319
I>2σ(I)
2375
1.089
R1 = 0.0100
wR2 = 0.0247
R1 = 0.0106
wR2 = 0.0251
0.363 and -0.495 e.A-3
I>2σ(I)
3831
1.093
R1 = 0.0161
wR2 = 0.0383
R1 = 0.0171
wR2 = 0.0386
0.851 and -0.508 e.A-3
I>2σ(I)
2738
1.121
R1 = 0.0238
wR2 = 0.0394
R1 = 0.0290
wR2 = 0.0401
0.652 and -1.385 e.A-3
I>2σ(I)
3627
1.054
R1 = 0.0233
wR2 = 0.0503
R1 = 0.0344
wR2 = 0.0534
1.012 and -0.590 e.A-3
1: Re(CO)3(bpz)Cl
θ range for data collection
Limiting indices
17
3: Re(CO)3(Me2bpz)Cl
Complex
Reflections collected /
unique
Completeness to θ = 26.00
Refinement method
Data / restraints /
parameters
Refinement threshold
Data > threshold
Goodness-of-fit on F2
Final R indices [I>2σ(I)]
R indices (all data)
Largest diff. peak and hole
2: Re(CO)3(bpz)(py).PF6
17
18
Figure 2.3. Crystal packing for [Re(CO)3(Me2bpz)(py).PF6] as seen down the 001 face.
18
2.2.2. Molecular Structures
Selected bond distances and angles are listed in Table 2.2. With the exception of one
bond length (Re-CEq), complex 1 has shorter Re-ligand bond lengths than its counterpart,
complex 2. Similarly, with the same exception, complex 3 had shorter bond lengths than its
counterpart, complex 4.
A comparison of Re-C bond lengths for complexes 3 and 4 to
complexes 1 and 2, respectively, revealed that one Re-CEq bond distance is longer by ~0.01 Å,
the other Re-CEq bond distance is approximately the same length, but the Re-CAx bond distance is
longer by ~0.02 Å.
19
Table 2.2. Calculated vs. X-Ray bond distances (Å) and selected angles (◦)
Complex
Re-N(L)
Re-N(L)
Re-CAx
Re-CEq
Re-CEq
Re-Cl
(L)N-Re-N(L)
C-Re-N(L)
C-Re-C
Complex
Re-N(L)
Re-N(L)
Re-N(Py)
Re-CAx
Re-CEq
Re-CEq
(L)N-Re-N(L)
C-Re-N(L)
C-Re-C
1: Re(CO)3(bpz)Cl
X-Ray
Calc.
Difference
2.150
2.178
0.028
2.151
2.178
0.027
1.902
1.927
0.025
1.917
1.942
0.025
1.937
1.942
0.005
2.484
2.550
0.066
75.21
75.18
-0.04
98.17
96.91
-1.26
89.86
90.33
0.47
.
2: Re(CO)3(bpz)(py) PF6
X-Ray
Calc.
Difference
2.161
2.189
0.028
2.162
2.189
0.027
2.202
2.250
0.048
1.920
1.951
0.031
1.927
1.944
0.017
1.933
1.944
0.011
75.03
75.09
0.06
96.38
97.29
0.91
90.02
90.20
0.18
20
3: Re(CO)3(Me2bpz)Cl
X-Ray
Calc.
Difference
2.158
2.181
0.023
2.177
2.181
0.004
1.924
1.925
0.001
1.922
1.940
0.018
1.917
1.940
0.023
2.460
2.550
0.090
75.34
75.20
-0.14
99.60
96.96
-2.91
87.85
90.33
2.48
4: Re(CO)3(Me2bpz)(py).PF6
X-Ray
Calc.
Difference
2.160
2.191
0.031
2.178
2.191
0.013
2.213
2.251
0.038
1.944
1.949
0.005
1.929
1.943
0.014
1.916
1.943
0.027
75.08
75.20
0.12
99.77
97.20
-2.57
90.08
90.31
0.23
2.2.3. Nuclear Magnetic Resonance Studies
NMR data and assignments of protons are given in Table 2.3 and their designations are
outlined in the figure below the table. The proton resonances of the pyridine ligand (protons 5, 6
and 7) were found upfield from those of the bipyrazine ligand (protons 1, 2 and 3). The
resonance for proton 1 is shifted downfield for Re(CO)3(Me2bpz)Cl compared to proton 1 for
Re(bpz)(CO)3Cl; proton 3, on the other hand, is shifted upfield. The methyl groups attached to
the bpz ring alters the ring current causing deshielding of proton 3 and shielding of proton 1.
Replacement of Cl- by pyridine in both bpz and Me2 bpz complexes gives rise to the same
observation, proton 1 is shifted downfield and proton 3 is shifted upfield. The shift for proton 1
is greatest for the pyridine adducts; the methyl groups attached to bipyrazine cause the greatest
shift for proton 3. The inductive affect of the methyl groups also causes a downfield shift of
proton 5 for the pyridinate complexes.
21
Table 2.3. NMR data with assignment of protons: Complex 1: Re(CO)3(bpz)Cl; Complex 2: Re(CO)3(bpz)(py).PF6;
Complex 3: Re(CO)3(Me2bpz)Cl; Complex 4: Re(CO)3(Me2bpz)(py).PF6
Proton
Complex
1
2
1
2
3
9.01, d,
9.15, dd
10.17, d,
(J = 2.8 Hz)
(J = 3.2, 1.2 Hz)
(J = 1.2 Hz)
9.15, d,
9.39, d,
(J = 3.2 Hz)
(J = 3.0, 1.0 Hz)
5
6
7
10.09, d,
8.47, d,
7.44, t,
7.99, t,
(J = 3.2 Hz)
(J = 4.8 Hz)
(J = 7.6 Hz)
(J = 7.2 Hz)
8.54, dd,
7.45, t,
7.99, t,
(J = 6.4, 1.2 Hz)
(J = 7.6 Hz)
(J = 7.0 Hz)
3
9.03, s
9.97, d,
4
9.28, s
9.89, d,
(J = 1.6 Hz)
(J = 1.6 Hz)
4
2.74, s
2.79, s
22
22
2.2.4. Infrared Studies
The energy of the carbonyl stretches for complexes 1 – 4 are listed in Table 2.4 and the
spectra are shown in Figure 2.4. As typical for rhenium(I) tricarbonyl complexes, three bands
were observed, although for complex 2 only a shoulder was discernable on the low energy
absorption manifold. For the pyridinate adducts, the bands for complex 2 shift to lower energy
compared to complex 1, but the absorption maxima for complex 4 shifts to higher energy
compared to complex 3.
Table 2.4. Experimental, calculated, and scaled carbonyl stretch frequencies (cm-1).
Exp.
Calc.
Scaled
Exp.
Calc.
Scaled
2049.0 1984.4 2026.7
2033.3 1981.6 2023.2
a
c
1939.0 1911.2 1936.3
1922.1 1906.5 1930.5
1
3
1915.8 1886.0 1905.3
1905.4 1881.7 1899.9
2037.2 2004.4 2051.3
2043.2 2001.7 2048.0
b
d
1938.3 1925.8 1954.3
1957.9 1920.7 1948.1
2
4
1924.1 1916.3 1942.6
.
a: Re(CO)3(bpz)Cl; b: Re(CO)3(bpz)(py) PF6; c: Re(CO)3(Me2bpz)Cl;
d: Re(CO)3(Me2bpz)(py).PF6
23
1
2
3
4
2150
2100
2050
2000
1950
1900
1850
1800
2150
-1
2100
2050
2000
1950
1900
-1
Wavenumber (cm )
Wavenumber (cm )
Figure 2.4. IR spectra of the carbonyl stretch region: (1) Re(CO)3(bpz)Cl, (2)
Re(CO)3(bpz)(py).PF6, (3) Re(CO)3(Me2bpz)Cl, (4) Re(CO)3(Me2bpz)(py).PF6
24
1850
1800
2.2.5. Absorption Studies
Absorption maxima and absorption coefficients are listed in Table 2.5 and absorption
spectra are shown in Figure 2.5. Metal-to-ligand charge transfer bands (MLCT) are assigned to
the low energy absorptions and π  π* to the absorptions at higher energy159b. Absorption
coefficients for the complexes range from 3240 – 4020 M-1cm-1 for the MLCT region and from
10540 – 20540 M-1cm-1 for the π  π* region. The MLCT maxima of the pyridine adducts were
blue-shifted with respect to their chloride derivatives and have higher absorption coefficients.
For the rhenium(I) Me2 bpz derivatives, the absorption spectra are less resolved, particularly for
complex 2 in the ultraviolet region and for complex 4 in the MLCT region. Three of the four
complexes show a unique, very sharp peak at around 350 nm. The reason for this peak is
unknown, but it is often observed in rhenium tricarbonyl complexes.
Table 2.5. Absorption data and assignments (Values in parenthesis are extinction coefficient)
π  π*a
MLCTa,b
236
308
336
420
1c
(17090)
(13730)
(8340)
(3240)
240
262
290
326
342
388
2c
(16130)
(14640) (13650)
(10920) (10540) (3740)
246
320
330
346
404
3c
(20540)
(14200)
(15090) (14700) (3340)
254
282
336
348
374sh
4c
(12050) (8750)
(8430)
(10430) (4020)
-1
-1
a: Data in nm (Data in M cm ); b: metal-to-ligand charge transfer; c: (1) Re(CO)3(bpz)Cl, (2)
Re(CO)3(bpz)(py).PF6, (3) Re(CO)3(Me2bpz)Cl, (4) Re(CO)3(Me2bpz)(py).PF6
Type of Transition
25
1.0
1
2
Normalized
0.8
0.6
0.4
0.2
0.0
Normalized
3
4
0.8
0.6
0.4
0.2
0.0
200
300
400
500
200
Wavelength (nm)
300
400
500
600
Wavelength (nm)
Figure 2.5. Experimental spectra (__) and scaled calculated spectra (---) in acetonitrile where (1)
Re(CO)3(bpz)Cl, (2) Re(CO)3(bpz)(py).PF6, (3) Re(CO)3(Me2bpz)Cl,
(4) Re(CO)3(Me2bpz)(py).PF6
26
2.2.6. Emission
The emission spectra were obtained at both room temperature and 77 K in 4:1
EtOH/MeOH. The emission maxima are listed in Table 2.6 along with emission quantum yields
and emission lifetimes. The room temperature emission spectra were very weak in intensity, so
all quantum yields are multiplied by 1000. Complexes 3 and 4 have larger quantum yields than
their counter part complexes 1 and 2, respectively. According to the quantum yields, complex 4
is the most intense and complex 1 is the weakest emitter at room temperature. When the
temperature of the solution was lowered to 77 K, the emission bands shifted ~50 nm to higher
energy and the emission intensity increased by a factor of 4-5.
Table 2.6. Emission maxima obtained by excitation at the MLCT maxima and excitation
maxima obtained from excitation spectra.
λex, 298 Ka
λex, 77 Ka λem, 298 Ka λem, 77 Ka Φ x 103 τ 298 Kb
1c
336, 423
339, 401
705
656
0.09
na
d
2
340, 392, 419 341, 390
684
632
1.72
25
e
3
346, 402, 423 348, 397
718
641
0.73
na
f
4
349, 390
349, 385
669
617
8.94
95
.
a: in nm; b: in ns; c: Re(CO)3(bpz)Cl; d: Re(CO)3(bpz)(py) PF6 ;
e: Re(CO)3(Me2bpz)Cl; f: Re(CO)3(Me2bpz)(py).PF6
τ 77 Kb
98
1522
2537
5507
Figure 2.6 shows normalized emission spectra at 77 K. The general shape remained the
same for all four complexes and no structure was observed. Further discussion about emission
properties will be given below.
27
1.0
Normalized
0.8
1
2
3
4
0.6
0.4
0.2
1.0
Normalized
0.8
0.6
0.4
0.2
0.0
500
600
700
800
900
Wavelength (nm)
600
700
800
900
Wavelength (nm)
Figure 2.6. Emission spectra at 77 K excited at the MLCT maxima where (1) Re(CO)3(bpz)Cl,
(2) Re(CO)3(bpz)(py).PF6, (3) Re(CO)3(Me2bpz)Cl, (4) Re(CO)3(Me2bpz)(py).PF6
28
2.2.7. Cyclic Voltammetry
Oxidation-reduction processes were determined by cyclic voltammetry and potentials are
listed in Table 2.7. Two reductions and one oxidation were observed. The first reduction was
reversible and assigned to reduction of the bpz ligand. The second reduction was irreversible
and assigned to reduction of rhenium(I) 162. An irreversible oxidation assigned to Re+  Re2+
was also observed162.
The first reduction and oxidation become more negative for the
dimethylated bipyrazine derivatives due to the electron donating characteristics of the methyl
substituents but more positive with replacement of chloride ion with pyridine.
Table 2.7. Oxidation and Reduction potentialsa
E½(V)b
Ep(V)b
Ep(V)b
Complex
LL0/Re+/0
Re2+/+
1: Re(CO)3(bpz)Cl
-0.76
-1.29
1.56
.
2: Re(CO)3(bpz)(py) PF6
-0.60
-1.30
2.07
3: Re(CO)3(Me2bpz)Cl
-0.94
-1.31
1.52
.
4: Re(CO)3(Me2bpz)(py) PF6
-0.79
-1.27
2.01
a: solvent is acetonitrile with 0.1 M TBAPF6, scan rate was 100 mV s-1
b: calculated by (Ep-En)/2
2.3. Discussion
2.3.1. Calculated Structures
As shown in Table 2.2, all the calculated bond distances were longer than those
determined by X-ray analysis which is common among metal complexes.
The difference
averaged 1.88 picometers for all bonds except the rhenium–chloride bonds which averaged 6.5
picometers.
Bond distances were also calculated for the analogues, Re(bpy)(CO) 3Cl,
Re(bpm)(CO)3Cl, [Re(bpy)(CO)3(py)]+ and [Re(bpm)(CO)3(py)]+, where bpy is 2,2’-bipyridine
and bpm is 2,2’-bipyrimidine. All the calculated coordinates are listed in the supplementary
29
information found in the APPENDIX A. The practice of using these minimized structures for
DFT and TDDFT calculations have been followed to obtain molecular orbitals, their energies
and molecular properties.
2.3.2. Molecular Orbitals
Figure 2.7 shows a graphical representation of the HOMO and LUMO for each of the
complexes and Table 2.8 lists the distribution of electron density in the molecules. The HOMO
for the chloro complexes contain ~40% dRe character with an equal distribution of electron
density (~40%) on Cl- and the remainder on the CO ligands. The HOMO of the pyridinate
complexes contain ~60% dRe character with ~20% of the electron density located on the CO
ligands and the remainder equally distributed over the pyridine and bipyrazine ligands. The
electron density on the LUMO, LUMO+1 and LUMO+2 in all cases, is centered on the
bipyrazine ligand (90%).
30
Figure 2.7. Graphical representation of optimized structure, HOMO orbital, LUMO orbital
where (1) Re(CO)3(bpz)Cl, (2) Re(CO)3(bpz)(py).PF6, (3) Re(CO)3(Me2bpz)Cl, (4)
Re(CO)3(Me2bpz)(py).PF6
31
Table 2.8. Electron distribution within the rhenium(I) molecules and their Mulliken charges
Ring
bpy
bpm
bpz
Me2bpz
bpy
bpm
bpz
Me2bpz
HOMO
Re
CO
41
19
40
19
40
18
40
18
Re
CO
63
24
63
24
63
23
63
24
Ring
1
1
1
1
Ring
8
8
8
8
Cl
39
40
41
41
Py
5
5
6
5
LUMO
Re
CO
2
4
2
4
3
5
3
5
Re
CO
2
4
2
4
4
5
3
5
32
Ring
93
93
90
90
Ring
93
93
91
91
Cl
1
1
2
2
Py
1
1
1
1
MC
0.454
0.500
0.475
0.463
0.826
0.884
0.849
0.841
The electron distribution and energies of bpy and bpm analogues were also examined for
comparison to the bpz and Me2bpz complexes. Details for these results are located in the
supplementary information section found in the APPEDNIX. Similar electron distributions were
found within the Cl and py series.
Mulliken charges on the rhenium center are also listed in Table 2.8. The charge nearly
doubles from 0.5 for the chloro complexes to 0.8 for the pyridinate species. The Mulliken
charge is greatest for the bpz and bpm complexes in accord with the greater π backbonding
associated with these ligands.
2.3.3. Molecular Orbital Energies
The energies of nine frontier occupied orbitals and nine frontier virtual orbitals for all
four complexes are shown in Figure 2.8. The energy gap for complexes 1 and 3 is ~2.6 eV; for
complexes 2 and 4 it is ~3.3 eV. These values correlate nicely with the absorption spectra
MLCT maxima.
The energy gaps for the chloro complexes Re(bpy)(CO)3Cl, Re(bpm)(CO)3Cl,
Re(bpz)(CO)3Cl, Re(Me2bpz)(CO)3Cl follow the series Re(bpy)(CO)3Cl (2.80 eV) >
Re(bpm)(CO)3Cl~Re(Me2 bpz)(CO)3Cl (2.65 eV) > Re(bpz)(CO)3Cl (2.53 eV). For the pyridine
complexes, the energy gaps fell in the series:
[Re(bpy)(CO)3(py)]+ (3.46 eV) >
[Re(Me2bpz)(CO)3(py)]+ (3.33 eV) > [Re(bpm)(CO)3(py)]+ (3.31 eV) > [Re(bpz)(CO)3(py)]+
(3.18 eV).
33
0
B (+8)
B (+8)
Re (+7)
CO (+6)
B (+7)
CO (+6)
L (+5)
L (+5)
B (+3)
B (+4)
B (+3)
B (+4)
-2
L (+2)
L (+2)
Energy, eV
-4
L (+7)
Py (+5)
Gap = 2.65 eV
Py (+3)
A (H)
A (-1)
A (-3)
L (L)
-10
A (-1)
C (-3)
L (+1)
L (L)
C (-4)
Cl (-5) L (-6)
L (-7) L (-8)
Gap = 3.33 eV
Gap = 3.18 eV
B (H)
B (-1)
B (-1)
B (-2)
L (-3)
L Py (-5)
-12
Py (+3)
L (+2)
B (-2)
A (-4)
A (-5)
L (-6) L (-8) L (-7)
B (+4) B P(+5)
L (+1)
B (-2)
-8
B (+6)
B (+6)
B (+4)
L (+2)
A (H)
CO (+8)
L (+7)
L (L)
CO (+8)
L (L)
Gap = 2.53 eV
-6
L (+1)
L (+1)
B (-2)
B (H)
L (-4) L (-3) L (-5)
Py (-6)
L (-4)
L Py (-6)
Py (-7)
Py (-7)
L (-8)
Py (-8)
-14
1
2
3
4
Complex
Figure 2.8. Molecular orbital energy diagram for nine frontier occupied orbitals and nine frontier
virtual orbitals of (1) Re(CO)3(bpz)Cl, (2) Re(CO)3(bpz)(py).PF6, (3) Re(CO)3(Me2bpz)Cl, (4)
Re(CO)3(Me2bpz)(py).PF6 in the singlet ground state in the gas phase. A = Re/CO/Cl, B =
Re/CO, C = Re/Cl, L = Ligand, Py = Pyridine
34
2.3.4. Absorption Spectra
After scaling, calculations of absorption spectra as shown in Figure 2.5 gave good
overlap for the calculated and experimental MLCT energy manifolds. A plot of the experimental
MLCT maxima versus the calculated MLCT maxima was linear. The least squares fit equation
was used to scale the calculated values which are listed in Table 2.9 along with the experimental
and calculated energies. All simulated spectra were determined in gas phase and acetonitrile; the
results obtained in acetonitrile were chosen for comparison.
Table 2.9. Experimental MLCT, calculated MLCT and scaled values.
MLCTa
λExp.
λCalc.
λScaledb
1c
420
476
419
d
2
388
439
390
e
3
404
458
405
f
4
374
417
373
a: in nm; b: see APPENDIX A; c: Re(CO)3(bpz)Cl; d: Re(CO)3(bpz)(py).PF6 ;
e: Re(CO)3(Me2bpz)Cl; f: Re(CO)3(Me2bpz)(py).PF6
Complex
The MLCT transition observed in the absorption spectra for complexes 1 and 3 occurs
from the HOMO-1 to the LUMO level. Whereas the MLCT absorption manifold for complexes
2 and 4 consists of transitions from two identical sets of orbitals separated by ~ 600 cm-1, the
HOMO-2 and HOMO, to the LUMO. These optical transitions are best labeled metal-ligand-toligand charge transfer (MLLCT).
35
2.3.5. Infrared Vibrational Spectra
The vibrational spectra were calculated as described in the experimental section and are
listed in Table 2.4. The values were all lower in energy then the experimentally determined
ones. The values were scaled by potting the energies of the experimental carbonyl stretches
versus the calculated values yielding a linear relationship. The least squares fit equation of the
points was used to obtain the scaled values which were in closer agreement with the
experimental determinations.
The calculated spectrum yielded some valuable information on the origin of the stretches.
There are three different stretches: a symmetric stretch which involves all three carbonyl groups,
an asymmetric stretch that also involves all three carbonyl groups, and a third asymmetric stretch
involving only the equatorial carbonyl groups. The lowest energy vibration for the two chloro
complexes is an asymmetric stretch involving all three carbonyl groups. The middle vibration
involves two carbonyl groups and the highest energy vibration is the symmetric stretch involving
all three carbonyl groups. For the pyridine bound complexes the two lower energy vibrations
switch places. The middle vibration becomes the asymmetric stretch involving all three carbonyl
groups and the lowest energy vibration involves two carbonyl groups.
A listing of carbonyl vibrational frequencies for various diimine complexes is given in
Table 2.10. The order of frequencies for the chloro complexes is: bpz>bpm,~Me 2bpz>bpy; the
order for the py complexes is: Me2bpz,~bpm>bpz>bpy. Complexes of bpm and Me2 bpz seem to
approximate each other in this comparison.
36
Table 2.10. Carbonyl stretch frequency comparison for 1 – 4 and similar compounds
Re(CO)3(bpy)Cl159
Re(CO)3(bpm)Cl162
Re(CO)3(bpz)Cl
Re(CO)3( Me2bpz )Cl
2022
2033
2049
2033
(sh)
1906(sh)
1939
1922
1890
1899
1916
1905
a
b
b
b
2026
2043(sh)
2037
2043
(sh)
2033
1906
1916
[Re(CO)3(bpy)(py)]+159
[Re(CO)3(bpm)(py)]+162
[Re(CO)3(bpz)(py)]+
[Re(CO)3( Me2bpz) (py)]+
1958
1938
37
a. CF3SO3- a. salt b. PF6- salt.
37
1924
2.3.6. Nuclear Magnetic Resonance
The electron density present on the bpz ring in the HOMO orbital primarily resides on the
2, 4, and 6 positions, leaving the 3 and 5 positions with much less. Consequently, the influence
of the methyl group located in position 5 on the ring system causes shielding of proton 3 with
little effect on the proton in position 6. Addition of pyridine has a similar effect on the proton
located in the 3 position but results in deshielding of protons in the 5 and 6 positions of the
bipyrazine rings. Hence, the resonance from these proton moves downfield.
2.3.7. Emission
Emission energies were calculated for the chloro and pyridinate complexes and are
tabulated in Table 2.11 and an energy level scheme is shown for the bpz complexes in Figure
2.9.
Least squares fit of the calculated vs. the experimental emission energies yielded an
equation which were used to determine scaled energies which are also listed in Table 2.11. The
scaled values were similar to the experimentally determined values.
38
Table 2.11. Experimental, calculated and scaled Emission Energies
Scaled
524
582
677
619
%Error
0.64%
0.28%
3.14%
3.49%
Pyridine Derivatives
Exp. Calc.
bpy
495 427
bpz
632 480
Me2bpz 617 467
Scaled
496
642
606
%Error
0.25%
1.55%
1.77%
-1
3
Energy (cm x 10 )
Chloride Derivatives
Exp. Calc.
bpy
521 500
bpm
584 532
bpz
656 584
Me2bpz 641 552
31
30
29
28
27
26
25
24
23
22
21
20
19
18
17
0.04
0.03
0.02
0.01
0.00
0.0
-0.01
3
LLCT
3
3
3
LLCT
LLCT
3
3
3
3
LMLCT
3
LMLCT
3
3
LMCT
dd
3
3
3
3
3
LMCT
LMCT
MLLCT
3
MLLCT
MLCT
3
3
LMLCT MLMLCT
G.S.
1
3
3
MLCT
MLLCT
dd
MLMLCT
3
MLLCT
1
3
3
LMLCT
MLMLCT
1
3
MLMLCT MLCT
LMLCT
LMLCT
3
3
LLCT
MLMLCT
3
MLLCT
1
G.S.
2
G.S.
3
1
G.S.
4
Complex
Figure 2.9. Calculated Triplet Excited States Relative to Ground States of (1) Re(CO)3(bpz)Cl,
(2) Re(CO)3(bpz)(py).PF6, (3) Re(CO)3(Me2bpz)Cl, (4) Re(CO)3(Me2bpz)(py).PF6.
39
2.3.8. Cyclic Voltammetry
We have previously reported46 that the first oxidation can be correlated with the HOMO
orbital energy to yield a straight line. Plots of Ep vs. the HOMO energy for the complexes
studied
here
along
with
data
for
Re(bpy)(CO)3Cl159
,
[Re(bpy)(CO)3py]+,159,
Re(bpm)(CO)3Cl162, and [Re(bpm)(CO)3py]+,162, where bpm is 2,2’-bipyrimidine were linear as
shown in Figure 2.10. Plots of the reduction potential versus the LUMO energies give similar
linear plots.
40
1.60
2.10
bpz
1.55
st
1 Oxidation (Volts)
2.05
bpz
Me2bpz
Me2bpz
2.00
1.50
1.95
1.45
1.90
1.40
1.85
1.35
1.80
bpy
bpy
1.30
-0.7
-6.5
-6.4
-6.3
-6.2
-6.1
-6.0
1.75
-5.9
-10.2 -10.1 -10.0
-0.6
bpz
-9.9
-9.8
-9.7
-9.6
-9.5
bpz
-0.7
-0.9
-1.0
Me2bpz
-0.8
bpm
-0.9
Me2bpz
bpm
-1.1
-1.0
-1.2
-1.1
st
1 Reduction (Volts)
-0.8
-1.3
bpy
bpy -1.2
-1.4
-4.0
-3.8
-3.6
-3.4
-3.2
-3.0 -7.0
Orbital Energy (eV)
-6.8
-6.6
-6.4
-6.2
-6.0
Orbital Energy (eV)
Figure 2.10. Correlation charts of HOMO vs. 1st Oxidation and LUMO vs. 1st Reduction.
Left: Chloride containing compounds: bpy-[Re(CO)3(bpy)Cl], bpm-[Re(CO)3(bpm)Cl] bpz[Re(CO)3(bpz)Cl] Me2bpz-[Re(CO)3(Me2bpz)Cl]; Right: Pyridine containing compounds: bpy{[Re(CO)3(bpy)(py)]+}, bpm-{[Re(CO)3(bpm)(py)]+}, bpz-{[Re(CO)3(bpz)(py)]+}, Me2bpz{[Re(CO)3(Me2bpz)(py)]+}.
41
2.4. Conclusion
Four new rhenium complexes containing two ligands: 2,2’-bipyrazine and 5,5’-dimethyl2,2’-bipyrazine have been described. Synthesis, spectroscopic and computational studies were
performed and analyzed.
The dimethyl bipyrazine ligand behaved, electronically, like a
bipyrimidine ring. The lifetime and quantum yields were greater for the methyl bipyrazine
derivatives, as well as blue shifts observed in the absorption spectra. The larger quantum yields
and remote nitrogen atoms could make these complexes useful for attachment to surfaces for
solar energy conversion devices.
42
CHAPTER 3
COMPARISON OF THE PROPERTIES OF [RU(2,2’-BIPYRIDINE)(6,6’-(1,2ETHANEDIYL)BIS-2,2’-BIPYRIDINE)]2+ AND [(RU(2,2’-BIPYRIDINE)2)2(6,6’-(1,2ETHANEDIYL)BIS-2,2’-BIPYRIDINE)]4+ TO [RU(2,2’-BIPYRIDINE)3]2+
3.1. Experimental
3.1.1. Materials
The ligand 6,6’-(1,2-ethanediyl)bis-2,2’-bipyridine163 (O-bpy), Ru(2,2’-bipyridine)Cl4164,
Ru(2,2’-bipyridine)2Cl2164 and Ru(2,2’-bipyridine)3(PF6)2164 were prepared as previously
reported. Optima grade methanol and tetraethylammonium chloride (TEACl) were purchased
from Fisher Scientific, while dry acetonitrile was purchased from Sigma-Aldrich.
AAPER
Alcohol and Chemical Co. was the source of absolute ethanol. Tetrabutylammonium perchlorate
was purchased from Southwestern Analytical Chemicals, Inc. and dried in a vacuum oven before
use. Ethanol and methanol were used in a 4:1 (v/v) mixture to prepare solutions for the emission
spectral and lifetime studies. Potassium ferrioxalate was synthesized by literature methods 165
using potassium oxalate and ferric chloride purchased from Fisher and Aldrich, respectively.
1,10-phenanthroline was obtained from G. F. Smith. Elemental analyses were determined by MH-W Laboratories, Phoenix, AZ.
3.1.2. Synthesis
[Ru(2,2’-bipyridine)(6,6’-(1,2-ethanediyl)bis-2,2’-bipyridine)]·2PF6: Ru(bpy)Cl4 (0.1 g, 251
μmol) and O-bpy (0.085 g, 251 μmol) were mixed in a 100 mL round bottom flask with 12 mL
of ethylene glycol. The mixture was brought to reflux for 1 hour. After cooling, a saturated
aqueous NH4PF6 solution (10 mL) was added followed by 50 mL of water. The solution was
stirred for 30 minutes and then filtered through a glass fritted filter. The solid was washed with
43
water and then ether. The solid was then dissolved in acetone and filtered to remove excess
NH4PF6. The acetone was removed slowly using a rotary evaporator. Suitable crystals for x-ray
analysis were grown from an acetone-water mixture, where the acetone was allowed to evaporate
leaving the crystals in the water phase. Yield = 80% (0.18 g, 200 μmol). 1H NMR (CD3CN): δ
ppm 2.88 (dd, 1H, J = 20, 8 Hz), 2.95 (dd, 1H, J = 16, 8 Hz), 3.36 (dd, 1H, 16, 8 Hz), 3.63 (dd,
1H, J = 20, 8 Hz), 6.81 (1H, d, J = 8 Hz), 7.21 (d, 1H, J = 8 Hz), 7.35 (m, 5H), 7.48 (d, 1H, J =
8Hz), 7.52 (d, 1H, J = 6Hz), 7.74 (d, 1H, J = 6Hz), 7.80 (t, 1H, 8Hz), 8.20 (m, 6H), 8.33 (d, 1H, J
= 8Hz), 8.37 (d, 2H, J = 8Hz), 8.53 (d, 1H, J = 8Hz), 8.62 (d, 1H, J = 8Hz). Anal. Calcd for
C32H26F12N6P2Ru: C, 43.40; H, 2.96; N, 9.49; Found: C, 43.78; H, 3.50; N, 9.99.
[(Ru(2,2’-bipyridine)2)2(6,6’-(1,2-ethanediyl)bis-2,2’-bipyridine)]·4PF6: Ru(bpy)2Cl2 (0.1 g, 207
μmol) and O-bpy (0.035 g, 104 μmol) were mixed in a 100 mL round bottom flask with 12 mL
of ethylene glycol. The mixture was brought to reflux for 1 hour. After cooling, a saturated
aqueous NH4PF6 solution (10 mL) was added followed by 50 mL of water. The solution was
stirred for 30 minutes and then filtered through a glass fritted filter. The solid was washed with
water and then ether. The solid was then dissolved in acetone and filtered to remove excess
NH4PF6. The acetone was reduced slowly on a rotary evaporator to ~ 10 mL. The concentrated
solution was added to swirling ether to precipitate the complex. Suitable crystals for x-ray
analysis were grown from a methanol/methylene chloride (50/50) solution which was allowed to
evaporate slowly. Yield = 80% (0.29 g, 166 μmol). 1H NMR (CD3CN): δ ppm 1.79 (td, 1H, J =
14, 4Hz), 1.89 (dd, 1H, J = 16, 10Hz), 2.20 (dd, 1H, J = 16, 10Hz), 2.61 (td, 1H, J = 14, 4Hz),
6.15 (d, 1H, J = 8Hz), 6.25 (d, 1H, J = 8Hz), 7.09 (t, 1H, J = 8Hz), 7.18 (t, 1H, J = 8Hz), 7.34 (m,
9H), 7.48 (m, 4H), 7.58 (d, 1H, J = 6Hz), 7.68 (m, 2H), 7.84 (m, 5H), 8.05 (m, 8H), 8.41 (m,
44
13H). Anal. Calcd for C62H50F24N12P4Ru2: C, 42.67; H, 2.89; N, 9.63; Found: C, 42.44; H, 3.06;
N, 9.40.
3.1.3. Physical Measurements
Absorption
measurements
were
determined
with
a
HP8452A
Diode
Array
spectrophotometer, and data was acquired with OLIS Global works software. All extinction
coefficients were determined in acetonitrile from Beer’s Law Plots. Fluorescence measurements
were obtained with a Spex Fluorolog 2:1:2 spectrofluorometer. The solvent for both room
temperature and 77 K studies was a fresh solution of 4:1 ethanol/methanol. The absorbance was
set to 0.1 at 450 nm for all complexes. All samples were degassed using the freeze-pump-thaw
method three or four times; residual gas had a pressure of ~ 150 mTorr. All NMR spectra were
obtained on a Varian 400 MHz spectrometer. The solvent was CD 3CN with TMS as an internal
standard.
Cyclic voltammograms were obtained in acetonitrile with 0.1 M tetrabutylammonium
perchlorate (TBAClO4) as the supporting electrolyte. A platinum metal disk was used for the
working electrode and a platinum wire functioned as the auxiliary electrode.
All
voltammograms were recorded versus a Ag/AgCl electrode. A PAR EG&G (Model 263A)
Potentiostat/Galvanostat was used to obtain the data and the PAR data interpreting program was
used to process the data.
Instrumentation for steady state photolysis consisted of a 100 watt xenon lamp (Oriel)
and a monochrometer. The light was directed into the cavity of the HP8452A Diode Array
spectrophotometer. The solution containing the compound of interest was irradiated in a 1 cm
cuvette at 450 nm, magnetically stirred, and its absorbance was observed at right angles to the
45
irradiating light. The intensity of the light source at the wavelength of excitation was determined
using potassium ferrioxalate as the actinometer following published procedures. 165
3.1.4. Computational Procedures
Calculations were effected using Gaussian ’03 (Rev. B.03)153 for UNIX. The molecules were optimized using Becke's three-parameter hybrid functional B3LYP154a with the non-local
term of Lee, Yang, and Parr154b and the local term of Vosko, Wilk, and Nassiar 154c. The basis set
SDD154d was chosen for all atoms, and the geometry optimizations were all ran in the gas phase.
TDDFT156 calculations were run in the gas phase utilizing the optimized singlet ground state
geometry.
50 transitional energies were calculated for the singlet states and 4 transitional
energies were calculated for the triplet states. All oscillator values and singlet and triplet excited
state values are presented in the supporting information found in the APPENDIX B.
3.1.5. X-Ray Analysis
The crystals were affixed to a nylon cryoloop using oil (Paratone-n, Exxon) and mounted
in the cold stream of a Bruker Kappa-Apex-II area-detector diffractometer160a. The temperature
at the crystals was maintained at 150 K using a Cryostream 700EX Cooler (Oxford
Cryosystems). The unit cell of [Ru(bpy)(O-bpy)](PF6)2 was determined from the setting angles
of 218 reflections; that of [(Ru(bpy)2)2(O-bpy)](PF6)4 was determined from the setting angles of
419 reflections.
Both were collected in 36 frames of data.
Data were measured with a
redundancy of 6.2 in the former and 5.4 in the latter using a CCD detector at a distance of 50 mm
from the crystal with a combination of θ and ω scans. A scan width of 0.5° and a time of 10
seconds in the former and 20 seconds in the latter were employed along with graphitemonochromated molybdenum Kα radiation (λ= 0.71073 Å) that was collimated to a 0.6 mm
46
diameter. Data collection, reduction, structure solution, and refinement were performed using
the Bruker Apex2 suite (v2.0-2)160a. All available reflections to 2θmax = 52° were harvested and
corrected for Lorentz and polarization factors with Bruker SAINT (v6.45) 160a. Reflections were
then corrected for absorption, interframe scaling, and other systematic errors with SADABS 160a
2004/1.
The structures were solved (direct methods) and refined (full-matrix least-squares
against F2) with the Bruker SHELXTL package (v6.14-1)160b. All non-hydrogen atoms were
refined using anisotropic thermal parameters for the O-bpy complex and all non-hydrogen atoms
were refined using anisotropic thermal parameters with a DELU restraint to deal with NPD’s for
the O-bpy dimer. All hydrogen atoms were included at idealized positions and not refined.
3.2. Results
3.2.1. Crystal Structure
The crystal structures for the [Ru(bpy)(O-bpy)]2+ and [(Ru(bpy)2)2(O-bpy)]4+ are shown
in Figure 3.1 and structural parameters are found in Table 3.1. The [Ru(bpy)(O-bpy)]2+ structure
has distorted octahedral geometry with varying bond distances around the ruthenium atom. The
distortions are also found in the [(Ru(bpy) 2)2(O-bpy)]4+. Two different isomers pack in racemic
pairs in the [Ru(bpy)(O-bpy)]2+ crystal, but this is not found in [(Ru(bpy)2)2(O-bpy)]4+, which
has only one type of ruthenium center. The hexafluorophosphate anions surround each of the
complexes and there is no solvent present in the unit cells.
47
48
Figure 3.1. Crystal structure of [Ru(bpy)(O-bpy)]2+ and [(Ru(bpy)2)2(O-bpy)]4+ (50% ellipsoids)161
48
Table 3.1. Crystal structure data collection information
Empirical formula
C32H26N6F12P2Ru
C62H50N12F24P4Ru2
Formula weight
Temperature
Wavelength
885.6
150 K
0.71073 Ǻ
1745.16
150 K
0.71073 Ǻ
Crystal system
Monoclinic
Triclinic
Space group
P21/c
P-1
Unit cell dimensions
a = 10.3470(4) Ǻ
a = 17.6231(14) Å
b = 25.3692(9) Å
b = 18.0032(15) Å
c = 12.2177(4) Å
c = 22.1267(16) Å
α = 90°
α = 91.997(5)°
β = 90.221(2)°
β = 107.362(4)°
γ = 90°
γ = 102.482(5)°
3
Volume
3207.1(2) Å
6504.7(9) Å3
Z
4
4
3
Calculated density
1.834 g/cm
1.782 g/cm3
Absorption coefficient
0.696 mm-1
0.685 mm-1
F(000)
1768
3480
Crystal size
0.34 x 0.09 x 0.04 mm
0.24 x 0.18 x 0.03 mm
Crystal habit
Needle
Needle
Crystal color
Lustrous Intense Red
Red
Reflections collected / unique
3.33 to 26.00
-12 ≤ h ≤ 12
-31≤ k ≤ 31
-15 ≤ l ≤ 15
56339 / 6281 [R(int) = 0.1056]
3.41 to 20.82o
-17 ≤ h ≤ 16
-18 ≤ k ≤ 17
0 ≤ l ≤ 22
13548 [R(int) = 0.0000]
Completeness to θ = 26.00
99.7 %
99.5 %
θ range for data collection
Limiting indices
o
2
Full-matrix least-squares on F2
Refinement method
Full-matrix least-squares on F
Data / restraints / parameters
6281 / 0 / 478
13548 / 666 / 1873
Refinement threshold
I>2σ(I)
I>2σ(I)
Data > threshold
3729
7492
1.000
1.063
Final R indices [I>2 σ (I)]
R1 = 0.0516, wR2 = 0.0812
R1 = 0.0901, wR2 = 0.1482
R indices (all data)
R1 = 0.1181, wR2 = 0.1020
R1 = 0.1833, wR2 = 0.1823
Goodness-of-fit on F
2
Largest diff. peak and hole
-3
0.830 and -0.516 e.A
49
0.688 and -0.717 e.A-3
3.2.2. Absorption Studies
The data in Table 3.2 lists the electronic transitions for the O-bpy complexes and the
parent, [Ru(bpy)3]2+. They all show three major transitions in acetonitrile. There is a transition
Table 3.2. Absorption data with extinction coefficients
Transitions, in nm (ε x 10-3 (M-1cm-1))
Complex
π → π*
MLCT
2+
[Ru(bpy)(O-bpy)]
246 (22.6) 290 (62.5)
454 (10.5)
4+
[(Ru(bpy)2)2(O-bpy)]
248 (44.7) 288 (137.7) 448 (23.9)
2+ a
[Ru(bpy)3]
250 (15.7) 288 (61.5)
450 (11.7)
a: Data from ref. 164
located at 246 nm for [Ru(bpy)(O-bpy)]2+, at 248 nm for [(Ru(bpy)2)2(O-bpy)]4+ and at 250 nm
for [Ru(bpy)3]2+ with extinction coefficients of 22,600, 44,700 and 15,700 M -1cm-1, respectively.
The next energy transition is located at 290 nm for [Ru(bpy)(O-bpy)]2+, at 288 nm for
[(Ru(bpy)2)2(O-bpy)]4+ and at 288 nm for [Ru(bpy)3]2+ with extinction coefficients of 62,500,
137,700 and 61,500 M-1cm-1, respectively. The MLCT region contained transitions centered at
454 nm for [Ru(bpy)(O-bpy)]2+, 450 nm for [Ru(bpy)3]2+ and 488 nm for [(Ru(bpy)2)2(O-bpy)]4+.
The extinction coefficients were 10,500 M -1cm-1 for [Ru(bpy)(O-bpy)]2+, 23,900 M-1cm-1 for
[(Ru(bpy)2)2(O-bpy)]4+ and 11,700 M-1cm-1 for [Ru(bpy)3]2+. Figure 3.2 shows that the spectra
for [(Ru(bpy)2)2(O-bpy)]4+ and [Ru(bpy)3]2+ are nearly identical in the MLCT region, but the
[Ru(bpy)(O-bpy)]2+ complex shows a broadening. Both of the O-bpy complexes show a
broadening in the π → π* region with respect to the band for [Ru(bpy) 3]2+.
50
1.0
Normalized
0.8
0.6
0.4
0.2
0.0
200
300
400
500
600
Wavelength (nm)
Figure 3.2. Experimental spectra for [Ru(bpy)3]2+ (black line), [Ru(bpy)(O-bpy)]2+ (blue line),
[(Ru(bpy)2)2(O-bpy)]4+ (red line).
51
3.2.3. Electrochemistry
Table 3.3 lists the oxidation and reduction potentials for the three complexes.
[Ru(bpy)3]2+ and [Ru(bpy)(O-bpy)]2+ underwent a one electron, reversible oxidation centered
around 1.28 V, but [(Ru(bpy)2)2(O-bpy)]4+ underwent a one two-electron, reversible oxidation
Table 3.3. Electrochemical dataa
Oxidationa
Reductiona
2+
3+
Ru → Ru
[Ru(bpy)(O-bpy)]2+
1.30
-1.26
-1.47
-1.77
2+
3+
Ru → Ru
[(Ru(bpy)2)2(O-bpy)]4+ 1.36
-1.25
-1.47
-1.75
Ru2+ → Ru3+ bpy→bpybpy→bpybpy→bpy2+ b
[Ru(bpy)3]
1.27
-1.31
-1.50
-1.77
1
a: All values in Volts, scan speed 100 mV s- , electrolyte is 0.1 M TBAPF6 in acetonitrile, b:
Data from ref. 164
Complex
centered at 1.36 V. Three one-electron reductions in the -1.25 to -1.8 V region were observed
for [Ru(bpy)3]2+ and [Ru(bpy)(O-bpy)]2+. Three two-electron reductions were found for
[(Ru(bpy)2)2(O-bpy)]4+. As noted in the past164, the bpy ligands for [Ru(bpy)3]2+ were reduced
sequentially. For [Ru(bpy)(O-bpy)]2+, the first two reductions were slightly more positive than
the corresponding ones for [Ru(bpy) 3]2+; the third occurred at the same potential, -1.77 V.
Similarly for [(Ru(bpy)2)2(O-bpy)]4+, three reversible reductions slightly more positive then for
[Ru(bpy)3]2+ were observed. Assignments of oxidation processes were made on the basis of DFT
studies as outlined below. With the exception of [Ru(bpy) 3]2+, it is not possible to make
definitive assignments for the three reductions associated with each of the ―bipyridine‖ units
since electron density is distributed over all of them in large, but unequal percentages (vide
infra).
52
3.2.4. Excited State Studies
Emission spectra are shown in Figure 3.3 and data are summarized in Table 3.4.
Emission maxima at room temperature were located at 599 nm for [Ru(bpy)(O-bpy)]2+, 601 nm
for [(Ru(bpy)2)2(O-bpy)]4+ and at 602 nm for [Ru(bpy)3]2+. Upon cooling to 77 K, the emission
Table 3.4. Emission data
Complex
λem,298a λem,77a
τ298b τ77b
Φ298a
Φ77a
Φpf
2+
[Ru(bpy)(O-bpy)]
599
578,620
e
9.55
0.0076 0.140
0.13
[(Ru(Bpy)2)2(O-Bpy)]4+ 601
582,628
e
6.00
0.0049 0.304
0.022
2+
c
d
[Ru(bpy)3]
602
574,621
0.82 5.05
0.064
0.384
0.051
a: 4:1 EtOH:MeOH, values in nm; b: μs; c: Ref. 164; d: Ref. 166; e: to weak to determine; f: 0.10
M TEACl in acetonitrile, Io = 7 X 1013 quanta/s
maximum for [Ru(bpy)(O-bpy)]2+ moved from 599 nm to 578 nm and had a vibrational band
maximum at 620 nm. For [(Ru(bpy)2)2(O-bpy)]4+, the emission band maximum shifted from 601
nm to 582 nm with a vibrational band at 628 nm and for [Ru(bpy) 3]2+ it moved from 602 nm to
574 nm with a vibrational band maximum at 621 nm. The vibrational band spacing increased in
the order: [Ru(bpy)(O-bpy)]2+ < [(Ru(bpy)2)2(O-bpy)]4+ < [Ru(bpy)3]2+ with energy spacings of
1170, 1260, and 1320 cm-1, respectively. The emission intensities of [Ru(bpy)(O-bpy)]2+ and
[(Ru(bpy)2)2(O-bpy)]4+ were weak at room temperature with quantum yields of 7.6 x 10 -3 and 4.9
x 10-3, respectively, so the lifetimes for these compounds were not determined. At 77 K the
emission lifetime of [Ru(bpy)(O-bpy)]2+ was 9.55 microseconds which is almost twice that of
[Ru(bpy)3]2+ (5.05 microseconds). [(Ru(bpy)2)2(O-bpy)]4+ had an emission lifetime of 6.00
microseconds which was very similar to that of [Ru(bpy) 3]2+. Using a standard curve167 the
emission quantum yields were obtained at 77 K. These were 0.140 for [Ru(bpy)(O-bpy)]2+ and
0.304 for [(Ru(bpy)2)2(O-bpy)]4+ compared to 0.384 for [Ru(bpy)3]2+.166 The quantum yields for
53
[Ru(bpy)(O-bpy)]2+ increased 18 fold from room temperature to 77 K and increased 62 fold for
[(Ru(bpy)2)2(O-bpy)]4+.
1.0
2+
[Ru(Bpy)3]
2+
[Ru(Bpy)(O-Bpy)]
4+
[(Ru(Bpy)2)2(O-Bpy)]
Normalized
0.8
0.6
0.4
0.2
0.0
550
600
650
700
Wavelength (nm)
750
800
Figure 3.3. Emission spectra at 77K for [Ru(bpy)(O-bpy)]2+ (blue), [(Ru(bpy)2)2(O-bpy)]4+ (red)
both normalized to [Ru(bpy)3]2+ (black)
54
3.3. Discussion
3.3.1. Geometry Study
The calculated bond distances listed in Table 3.5 are slightly larger than the experimental
numbers consistent with reports in the literature resulting from gas phase calculations. 147,148
Both O-bpy molecules are distorted into unusual confirmations which were modeled effectively
by the calculations. Despite the distortions, the majority of the Ru-N bond distances are similar
to those of [Ru(bpy)3]2+ (Ru-N = 2.057 Å). For [Ru(bpy)(O-bpy)]2+ experimentally bonds 3 and
6 are the shortest; bonds 4 and 5 are similar to the Ru-N bond distances found for [Ru(bpy)3]2+.
For [(Ru(bpy)2)2(O-bpy)]4+ the 6 and 6’ bonds are the longest due to attachment of the ethyl
group.
55
Table 3.5. Bond distances (Å) and scheme showing bond locations
[Ru(bpy)(O-bpy)]2+
Calc.
Exp.
Δ
[(Ru(Bpy)2)2(O-Bpy)]4+
Calc.
Exp.
Δ
Calc.
Exp.
Δ
[Ru(bpy)3]2+ a
Calc.
Exp.
Δ
1
2
3
4
5
6
2.112
2.086
0.026
1
2.183
2.079
0.104
1’
2.104
2.051
0.053
1
2.091
2.057
0.034
2.104
2.067
0.037
2
2.089
2.062
0.027
2’
2.097
2.043
0.054
2
2.091
2.057
0.034
2.070
2.023
0.047
3
2.093
2.068
0.025
3’
2.089
2.062
0.027
3
2.091
2.057
0.034
2.111
2.068
0.043
4
2.100
2.041
0.059
4’
2.093
2.057
0.036
4
2.091
2.057
0.034
2.108
2.067
0.041
5
2.081
2.056
0.025
5’
2.081
2.040
0.041
5
2.091
2.057
0.034
2.095
2.065
0.030
6
2.196
2.116
0.080
6’
2.202
2.149
1
0.053
6
2.092
2.057
0.035
a: Data from Ref. 147
N
N
1
N
N
2
3
N
1
N
6
Ru
6
N
5
N
4
5
N
N
C
H2
CH2
N
N
N
N 3 2
N
3
Ru
4
N
4
N
2
Ru
5
6'
N
1
6
5'
N 1'
N
4' N
Ru
2'
3'
N
N
N
56
The distortion can be evaluated in two ways. First, the angles of coordinating atoms
about the axes listed in Table 3.6 are examined. Their location on the molecules is shown in
Figure 3.4 and a schematic of the angles is shown in Figure 3.5. The two O-bpy derivatives will
be compared to [Ru(bpy)3]2+. The angle BMC, AMF, and EMD belong to the five member ring
formed by the bipyridine molecules and is consistently 79.03 degrees for [Ru(bpy)3]2+. For
[Ru(bpy)(O-bpy)]2+, three different values are obtained: 80.19°, 77.32° and 78.63°. Similarly for
[(Ru(bpy)2)2(O-bpy)]4+ the values are 78.45°, 79.71°, and 79.02°. The other angles in the table
show how the molecule is further distorted from the geometry of [Ru(bpy) 3]2+. Interestingly, the
largest angle of >100° for [Ru(bpy)(O-bpy)]2+ and [(Ru(bpy)2)2(O-bpy)]4+ differ in their location
but are the result of the ethyl bridge. In [Ru(bpy)(O-bpy)]2+ the location of the angle is between
pyridine ring remote to the ethyl bridge and another pyridine ring in the molecule; in
[(Ru(bpy)2)2(O-bpy)]4+ it is located between the pyridine ring adjacent to the ethyl bridge and
another pyridine ring in the dimer.
57
Table 3.6. Angles (◦) describing the octahedral geometry around the ruthenium center
Angle (°) [Ru(bpy)3]2+ [Ru(bpy)(O-bpy)]2+ [(Ru(bpy)2)2(O-bpy)]4+
95.91
98.01
104.23
AMB
79.03
80.19
78.45
BMC
95.91
98.86
94.99
CMD
89.55
84.67
82.64
DMA
79.03
77.32
79.71
AMF
95.91
91.24
94.76
FMC
89.55
91.41
91.61
CME
95.91
100.40
93.54
EMA
89.55
95.91
79.03
95.91
FMB
BME
EMD
DMF
a: M is Ru
97.35
92.67
78.63
91.36
90.91
97.50
79.02
93.16
D
A
F
B
E
F
Ru
Ru
C
D
A
C
E
B
C
H2
CH 2
N
A
D
N
F
Ru
N
H2C
CH 2
Ru
N
E
N
B
C
N
Figure 3.4. Schematic drawing of the molecules with letters corresponding to the angles in
Table 3.5
58
F
A
A
A
F
D
M
B
=
D
M
B
+
D
M
B
+
E
M
F
E
C
E
C
C
Figure 3.5. Schematic drawing of the bond angles
Secondly, the distortion can be ascertained based on the twist about the pyridine rings in
the ―bipyridine‖ unit. Table 3.7 lists the dihedral angles determined from the selected atoms
shown in Figure 3.6. The dihedral angles for the three bipyridine ligands on [Ru(bpy) 3]2+ were
all found to be 9.97°. This measure describes the angle between the pyridine units of a given
bipyridine ring which affects π electron delocalization over the rings. Using [Ru(bpy) 3]2+ as a
reference point, the bipyridine ring in [Ru(bpy)(O-bpy)]2+ is ~ 1° more twisted, but the four
bipyridine ligands on [(Ru(bpy)2)2(O-bpy)]4+ are much flatter with angles of -3.56°, 2.77°, -2.72°
and 1.35°. The two parts of the O-bpy ligand have angles of 9.17° and -8.21° for [Ru(bpy)(Obpy)]2+ and angles of 12.34° and 15.83° for [(Ru(bpy) 2)2(O-bpy)]4+.
59
F
G
E
B
N
N
H
C
A
N
N
CH2
X
D
Figure 3.6. Scheme showing the two rings systems and the atoms selected to measure the
dihedral angle
Table 3.7. Dihedral angles (◦) for each of the ligands present on each molecule
Dihedral
ABCD
EFGH
[Ru(bpy)3]2+
9.97
9.97
9.97
n.a.
[Ru(bpy)(O-bpy)]2+
-11.00
9.17
-8.21
[(Ru(bpy)2)2(O-bpy)]4+
-3.56
2.77
-2.72
1.35
12.34
15.83
The combination of the dihedral angles of the bipyridine residues and the angles of atoms
about the axes are important in helping to understand the properties of the complexes discussed
in subsequent sections.
Overall, there is a greater distortion about the axes observed for
[Ru(bpy)(O-bpy)]2+ than [(Ru(bpy)2)2(O-bpy)]4+ and greater dihedral distortion.
3.3.2. Molecular Orbitals
The HOMO and LUMO orbital diagrams, Figure 3.7, along with the percent contribution
show that the HOMO is dominated by the ruthenium and the LUMO is dominated by the ligands
attached. The main difference is the distribution of electron density in the LUMO orbital
diagrams, Table 3.8 and Figure 3.8. In [Ru(bpy) 3]2+each of the bipyridine ligands has an equal
share, but with the [Ru(bpy)(O-bpy)]2+ complex 57% of the electron density resides on the
60
bipyridine ligand and 42% on half of the O-bpy ligand. [(Ru(bpy)2)2(O-bpy)]4+ shows a similar
distribution with 68% of the electron density residing on the bipyridine ligand and 30% on the Obpy ligand. Due to the distortion and the puckering of the rings some of the π orbital levels have
increased in energy causing the uneven distribution of electron density seen in the LUMO
orbital.
61
Figure 3.7. HOMO and LUMO orbital diagrams
62
Table 3.8. Table of percent contributions of each species for the LUMO+2 to the HOMO-2
energy levels
Species
[Ru(bpy)(O-bpy)]2+
[(Ru(bpy)2)2(O-bpy)]4+
[Ru(bpy)3]2+
Species
[Ru(bpy)(O-bpy)]2+
[(Ru(bpy)2)2(O-bpy)]4+
[Ru(bpy)3]2+
HOMO-2
Ru bpy
79 5
79 13
75 25
LUMO
Ru bpy
1
57
2
68
0
100
O-bpy
16
8
O-bpy
42
30
-
HOMO-1
Ru bpy
79 7
76 19
75 25
LUMO+1
Ru bpy
5
0
5
31
6
94
O-bpy
14
5
O-bpy
95
63
-
HOMO
Ru bpy
72 9
81 13
82 18
LUMO+2
Ru bpy
9
39
5
91
6
94
O-bpy
19
7
O-bpy
52
4
-
100
90
80
% Contribution
70
60
50
40
30
20
10
0 HOMO -2
HOMO -1
HOMO
LUMO
LUMO +1
LUMO +2
Orbital
Orbital
Figure 3.8. Graphical representation of the orbital contributions: Red – Ruthenium orbitals,
Green – O-bpy, Blue – bpy. The order of the columns in each set of three is [Ru(bpy) 3]2+,
[Ru(bpy)(O-bpy)]2+, [(Ru(bpy)2)2(O-bpy)]4+
63
3.3.3. Absorption Studies
Shown in Figure 3.9 are the simulated and experimental absorption spectra for the
[Ru(bpy)(O-bpy)]2+ complex. The simulated spectrum was calculated in the gas phase and
closely agrees with the experimental spectra. Previously, we147,148 and others149,150 have reported
the need to make corrections for the solvent, but in this case it appeared unnecessary to do so.
The difference in energy levels appears to remain the same in solution as in the gas phase. The
low energy band maximum is the same for both the experimental and calculated spectra, 454 nm.
The π to π* transition for the experimental spectrum is found at 290 nm, where it is blue shifted
for the calculated spectrum by 12 nm. The shoulder located at 360 nm in the calculated spectrum
is not resolved in the experimental one.
64
4
Extinction Coefficient
7x10
4
6x10
4
5x10
4
4x10
4
3x10
4
2x10
4
1x10
0
250
300
350
400
450
500
550
600
Wavlength (nm)
Figure 3.9. Simulated (----, gas phase) and experimental (―, acetonitrile) absorption spectra for
[Ru(bpy)(O-bpy)]2+
65
Assignments of the absorption bands were obtained from the TDDFT output file. The
frontier orbital energies of the [Ru(bpy)(O-bpy)]2+ complex are compared to those of
[Ru(bpy)3]2+ in Figure 3.10.
The degeneracy of the bipyridine ligands is removed in the
[Ru(bpy)(O-bpy)]2+ complex. The figure shows that the higher energy transitions, most likely π
→ π*, will originate from the O-bpy ligand and not the bipyridine as in the parent complex. The
LUMO orbitals are ligand centered (LC); the HOMO orbitals are largely dRu based (70 – 80%)
with added LC orbital character. Hence the low energy transition is MLLCT in character.
66
-52
-56
-60
-64
L+4,+5
L+3
O-Bpy
LC
L+4,+5
L+3
Bpy
Bpy
L+2
L+1
LUMO
LC
O-Bpy
LC
LUMO,+1,+2
Bpy
-1
3
Energy (cm x 10 )
-68
-72
-76
Gap = 26,370
Gap = 25,970
-80
L+4,+5
L,+1,+2,+3
-84
-88
HOMO,-1,-2
Bpy
LC
Ru
HOMO,-1,-2
Ru
-92
-96
-100
H-3,-4,-5
Gap = 25,730
O-Bpy
H-3 to H-5
Bpy
-104
-108
HOMO,-1,-2
H-3,-4,-5
-112
Ru
Ru
-116
-120
[Ru(bpy)(O-bpy)]
2+
[(Ru(bpy)2)2(O-bpy)]
4+
[Ru(bpy)3]
2+
Figure 3.10. Frontier orbital energy diagram for the six occupied (HOMO to HOMO-5) and six
virtual orbitals (LUMO to LUMO+5).
67
3.3.4. Emission Spectra
The calculated emission transition energies are given in Table 3.9. Four triplet transitions
were calculated, but only the first transition for each is listed; the other three can be found in the
Table 3.9. Calculated emission data
Compound
[Ru(bpy)(O-bpy)]
Calculated Transitions
Singlet Triplet Energy Gapa
2+
Ru(0.6)
[(Ru(bpy)2)2(O-bpy)]
4+
Singlet Triplet Energy Gapa
bpy(1.0)
[Ru(bpy)3]
2+
Ru(0.7)b
→
bpy(1.0)b
→
Singlet Triplet Energy Gapa
bpy(1.0)
bpy(1.0)b
→
Energy (cm-1)
17,200
Assignment
3
MLCT
3
18,200
17,600
3
17,700
18,400
MLCT
3
18,400
3
d-d
ILCT
MLCT
3
ILCT
a: Difference in energy between singlet state energy and triplet state energy; b: values in
parenthesis are the percent contribution
supplementary information found in the APPENDIX B. The singlet-triplet energy gap was
determined by subtracting the energy of the triplet state from the energy of the singlet state. For
[Ru(bpy)(O-bpy)]2+ the calculated value was 17,200 cm-1 ; for [Ru(bpy)3]2+ it was 17,700 cm-1;
for [(Ru(bpy)2)2(O-bpy)]4+ it was 17,600 cm-1. Due to the similarity of the [(Ru(bpy) 2)2(Obpy)]4+ and [Ru(bpy)3]2+ only the [Ru(bpy)3]2+ results will be discussed. The experimental
emission values at 77 K are 17,300 cm-1 and 17,400 cm-1 for the [Ru(bpy)(O-bpy)]2+ and
[Ru(bpy)3]2+, respectively. The experimental transitions for all three are averaged in the left hand
side of Figure 3.11 and are compared to states derived by calculation for each molecule on the
right hand side. The dashed line in Figure 3.11 is a reference line for the experimentally
observed energy gap. The lowest lying triplet excited state for [Ru(bpy)3]2+ and [(Ru(bpy)2)2(O-
68
bpy)]4+ is the 3MLCT state; hence the
3
MLCT  1GS follows accepted assignments. The
difference in their emission quantum yields at room temperature can be accounted for on the
basis of the structure of [(Ru(bpy)2)2(O-bpy)]4+ where the possibility of self quenching exists.
The distance between the Ru centers is only 8.14 Å and between the O-bpy ligand and one
bipyridine ligand on the other metal center is only 3.46 Å (S5).
For [Ru(O-bpy)(bpy)]2+, however, the
3
MLCT lies lower in energy than the observed
experimental energy; hence population of the lowest energy excited state, the 3dd, occurs. This
would seem to indicate that there should be no emission from the complex, but that is not the
case. If the 3MLCT were populated directly, one might expect the emission intensity to be
reduced by a factor of 3 since statistically only one bpy ligand is coordinated to [Ru(bpy)(Obpy)]2+ which contains the lowest lying π* orbital. However, at room temperature, the emission
is 100 times weaker than for [Ru(bpy) 3]2+. Vibronic overlap between the 3dd and 3MLCT state
may be the mechanism leading to the observed emission. The 3dd state plays a significant role as
noted by the large Cl- substitution quantum yield.
69
Exp.
[Ru(bpy)3]2+ [Ru(bpy)(Obpy)]2+ [(Ru(bpy)2)Obpy]4+
18.4
3ILCT
Emission Energy (cm-1x103)
18.4
3ILCT
17.3
3MLCT
18.2
3d-d
17.7
3MLCT
17.6
3MLCT
17.2
3MLCT
X
1G.S.
1G.S.
1G.S.
1G.S.
Figure 3.11. Diagram showing the calculated emission energy in relation to the experimental
energy
70
[Ru(bpy)(O-bpy)]2+ and [(Ru(bpy)2)2(O-bpy)]4+ were found to undergo photosubstitution
in the presence of Cl- just as has been reported for [Ru(bpy)3]2+.168 The quantum efficiency for
Cl- photosubstitution at λex = 436 nm for [Ru(bpy)(O-bpy)]2+ is approximately 3 times greater
than for the other two compounds (Table 3.4). Further investigation into this reaction is ongoing.
3.4. Conclusion
The addition of an ethyl bridge between two of three bipyridine ligands for [Ru(bpy)3]2+
altered the geometry of the complex from D3 to C2 or lower. The absorption properties were
similar, but the emission and photostability of the complex underwent a significant change.
Population of the 3MC state in [Ru(bpy)(O-bpy)]2+ lowered the emission intensity at room
temperature and its population resulted in rapid photosubstitution.
71
CHAPTER 4
SOLUTION AND PHYSICAL PROPERTIES OF IRON(II) TRIS 2,2’-BIPYRAZINE:
KINETICS AND DFT CALCULATIONS
4.1. Experimental
Iron(II) tris-bipyrazine was generously provided by the Julve group in an earlier study, 137
was received in crystalline form and used without further purification. Solvents were purchased
from Aldrich and used without purification. Dry acetonitrile was purchased from Aldrich and
used for absorption studies. Tetraethylammonium chloride (TEACl) and tetrabutylammonium
thiocyanate (TBASCN) were obtained from Aldrich. Tetrabutylammonium bromide (TBABr)
was obtained from Eastman.
Calculations were effected using Gaussian ’03 (Rev. B.03) for UNIX153. The molecules
were optimized using Becke's three-parameter hybrid functional B3LYP154a with the non-local
term of Lee, Yang, and Parr154b and the local term of Vosko, Wilk, and Nassiar 154c. The basis set
SDD154d was chosen for all atoms. Raw data shown in APPENDIX C.
The absorption data was obtained using a HP8452A UV/Vis Spectrophotometer. Olis
Global Works Software and Origin 6.1 were used to analyze and process the data. The solvent
used was dry acetonitrile.
An Olis RSM 1000 Spectrophotometer equipped with a U.S.A. Stopped Flow Reactor
was used to collect all kinetic data. The change in absorbance of the solution containing
Fe(bpz)32+, conc. 2 x 10-4 M, was recorded at 508 nm as a function of time. The iron containing
solution and the acetonitrile solutions containing the anions Cl-, Br- and SCN- were mixed in a
1:1 ratio within the instrument. The acetonitrile solutions were 0.01 TEACl, 0.01 M TBASCN
and 0.01 TBABr. Concentration studies were performed by diluting the analytes before reaction.
72
Temperature was controlled by a Jasco temperature controller maintained at 25°C for the
concentration dependent measurements, but varied for thermodynamic property determinations.
4.2. Results
The optimized structure in the gas phase was obtained using the calculation method
described in the experimental section and compared here in Table 4.1 to the crystal structure
showing the accuracy of the calculation. The bond lengths were an average of 4.8 picometers
longer; this is in agreement with gas phase calculations for metal complexes found by us 147,148,169
and others170-172. The calculated angles also were comparable to the crystal structure data.
Overall the optimized molecule mimics the actual molecule in acceptable agreement for
performing the additional theoretical calculations below.
Table 4.1. Comparison of crystal structure to calculated bond distances and angles
Fe-N Bonds (Ǻ)
Crystal Calc.
1.967
2.011
1.953
2.002
1.966
2.011
1.961
2.011
1.957
2.010
1.966
2.011
Average
Δ
0.044
0.049
0.045
0.050
0.053
0.045
0.048
N-Fe-N Angles (◦)
Crystal Calc.
Bpz 81.80
80.93
Bpz 81.53
80.92
Bpz 81.44
80.90
E-A 92.84
93.10
E-A 92.92
93.11
Δ
0.87
0.61
0.54
0.26
0.19
Average
0.49
The absorption spectrum shown in Figure 4.1 was obtained in dry acetonitrile. The
extinction coefficients were determined from Beer’s Law plots by dissolving a sample in dry
acetonitrile and diluting it just before the spectrum was taken. The values are shown in the insert
of Figure 4.1.
73
1.0
0.9
Absorbance
0.8
λ
ε (M-1cm-1)
510
7700
482
6200
310
40000
0.7
270
21000
0.6
238
30000
0.5
0.4
0.3
0.2
0.1
0.0
200
300
400
500
600
Wavelength (nm)
Figure 4.1. Absorption spectrum of Fe(bpz)32+ in acetonitrile
Table 4.2 lists energy maxima for several iron(II) and ruthenium(II) diimine complexes.
The energy maxima of the metal-to-ligand charge transfer (MLCT) maxima of the iron(II)
complexes fall in the order Fe(bpz)32+ > Fe(phen)32+ > Fe(bpy)32+.
The MLCT energy
maxima164,173 of the ruthenium(II) complexes follow a similar pattern, Ru(bpz) 32+ > Ru(phen)32+
> Ru(bpy)32+ but are blue shifted from their iron(II) congeners by approximately 3,000 cm-1.
The π → π* transitions located in the 30,000 cm-1 region follow a similar pattern with the
ruthenium(II) complexes maxima blue shifted from their iron(II) analogues.
74
Table 4.2. Absorption band comparison [υ / 103 cm-1]
Complex
π → π* MLCT
Fe(bpz)32+ a
32.2
19.6
2+ b
Fe(bpy)3
32.7
19.2
Fe(phen)32+ b
19.4
2+ c
Ru(bpz)3
34.4
22.7
2+ c
Ru(bpy)3
35.1
22.2
2+ d
Ru(phen)3
22.4
a: in acetonitrile, b: in DMF-(TBA)BF4 (Ref. 139)
c. in acetonitrile (Ref. 164); d. in acetonitrile (Ref. 173)
4.3. Kinetic study
When crystals of Fe(bpz)32+ were added to water, the solution around the crystals was red
but the rest of the solution was colorless, even after mixing. The color change also occurred
upon addition of water to an acetonitrile solution containing the complex as shown in Figure 4.2.
Upon dilution of an acetonitrile solution by adding an equal amount of water, the absorbances in
the 320 and 500 nm regions decreased and one at 288 nm increased over a 3 minute period as
shown in the figure. Isosbestic points were observed at 299, 265, 231 and 211 nm indicating a
smooth reaction from reactant to product. Upon completion of the reaction, all the coordinated
bipyrazine ligand had been removed as deduced from its absorbance at 288 nm (ε = 19,500 M1
cm-1).174
75
1.4
1.4
1.2
Absorbance
1.2
Absorbance
1.0
0.8
1.0
0.8
0.6
0.6
0.4
0.4
0.2
200
225
250
275
300
325
Wavelength (nm)
0.2
0.0
200
250
300
350
400
450
500
550
Wavelength (nm)
Figure 4.2. Series of absorption data taken for the reaction of Fe(bpz)32+ with water , the red line
shows the absorption after 3 minutes. (Insert: Expanded region from 200 to 325 nm, blue circles
indicate isosbestic points.)
The iron complex is attacked by the water molecule and complete dissociation of
coordinated bipyrazine occurs. Rather than determine the kinetics of the water reaction, we
chose to investigate the reaction of Fe(bpz) 32+ with simple anions in acetonitrile. The five anions
chosen were: F-, Cl-, Br-, I-, and SCN-. The reaction with fluoride was too fast on the stoppedflow time scale to study, even at low temperatures, and addition of iodide caused the diiodide salt
to precipitate from solution. The other three anions remaining for study, bromide, thiocyanate
and chloride, varied in size and reactivity with the iron complex.
The data shown in Figure 4.3 for the reaction of the iron complex with chloride ion in
acetonitrile was obtained in 1 second using a stopped flow apparatus. As found for the water
reaction, the absorbance decreased in the 500 nm region to baseline concurrent with removal of
the bipyrazine ligands.
76
0.14
Absorbance
0.12
0.1
0.08
0.06
0.04
0.02
0
450
475
500
525
550
575
600
Wavelength (nm)
Figure 4.3. Graphs obtained from the reaction of Fe(bpz)32+with chloride ion over 1 second,
each trace represents 0.125 seconds
When the absorption change data is plotted in three dimensions vs. time and wavelength
as shown in Figure 4.4, the peak at 508 nm disappears and there are no side reactions or peaks
that appear. The figure verifies that complete loss of MLCT band.
77
0.14
0.12
0.1
Absorbance
0.08
0.06
0.04
0.02
451
479
0
0
Tim
e (S
564
ec)
508
)
(nm
536 length
ve
Wa
593
1
Figure 4.4. Expanded 3-dimensional view of the data shown in Figure 4.3
Decay curves for the reaction of Fe(bpz)32+ with Cl-, Br-, and SCN- are shown in Figure
4.5. The curves are exponential with the reaction rate for Cl- > SCN- > Br -. Values for kobs at
0.008 M were obtained from the decays and are listed in Table 4.3.
Table 4.3. Rate constants and thermodynamic data
Analyte
BrSCNCl-
Ki
kobs
(M-1s-1)
1.719 244.82
4.876 211.96
12.321 233.77
k3
(s-1)
2.606
7.739
18.881
∆H‡
(kJ mol-1)
138.4
97.6
116.3
78
∆S‡
(J mol-1 K-1)
225
95.8
166
∆G‡
(kJ mol-1)
72.1
69.1
66.8
Normalized Absorbance
1.0
Bromide
Chloride
Thiocyanate
0.9
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0.0
0.0
0.2
0.4
0.6
0.8
1.0
Time in Seconds
Figure 4.5. Decay curves for the three analytes when reacted with Fe(bpz)32+ in acetonitrile
A plot of kobs versus the concentration of analyte was nonlinear as shown in Figure 4.6
which fit the mathematical expression given in equation 1. 175 The data for Ki and k3 are listed in
Table 4.4.
k
obs

k K [Y ]
K [Y ]  1
3
i
i
i
(4.1)
i
kobs : observed rate constant
Ki : rate constant for the first step (Product of k1/k2)
k3 : rate constant for the third step
[Yi] : concentration of analyte
This rate law corresponds to a reaction that has a preassociation step and then a
substitution step as given by equation 4.2. Ki is very similar and large for all three analytes
indicating the preassociation lies in favor of the ion pair. The substitution rate constant, k 3, is
largest for the reaction with Cl-, then NCS -, and then Br -.
79
k3 R - Y + X
Ki   R - X +Y  
R - X + Y 
R-X : iron complex (Fe-N)
Y : analyte being studied
Figure 4.6. kobs vs. anion concentration for the reaction of Fe(bpz)32+ with chloride
80
(4.2)
Thermodynamic parameters were determined from temperature dependent studies. The
activation energy, G‡, corresponds to the trends found for the observed and calculated rate
changes between the three anions. The activation enthalpies and entropies follow the sequence
NCS- < Cl- < Br-. This variation for Cl- and Br - can be related to size differences. It is not clear
why NCS- has the lower values, although it may be related to the ambidentate nature of the
ligand.
Figure 4.7 shows a proposed reaction mechanism using the reaction with Br - as an
example.
The first step is the preassociation step involving anion recognition by the iron
complex forming an ion pair in solution. The dashed line indicates an attraction occurs between
the iron complex and the anion. Substitution occurs in step two forming a bond between the
metal center and the anion while simultaneously breaking one of the iron nitrogen bonds
resulting in a monodentate bipyrazine ligand. At this point there are two options: 1. attack by a
second bromide ion can occur, or 2. a change of spin state from low spin to high spin iron can
occur. The change in spin state is entirely possible given that the magnetic moment of
Fe(bpz)32+ is reported to be 0.7 B.M. This places the tris-chelate at the cross-over point of a
Tanabe-Sugano diagram. (This argument will be strengthened in the calculated mechanism.)
The high spin state then triggers rapid reactions leading to the final solvated product. The color
of the solution at the end of the reaction is pale yellow indicative of the iron dibromide species.
81
N
N
N
N
N
N
Ki
N
+Br
N
Br
N
N
N
N
N
82
N
N
N
N
N
N
C
N
N
N
H3C
N
N
Br
Fe
N
N
N
Br
N
Fe
N
-Br-
N
N
Br
Br
Fe
N
C
N
Br
Fe
N
CH3
CH3
S=2
N
S=2
N
Figure 4.7. Purposed mechanism for the reaction of Fe(bpz)32+ with an anion
82
S=2
C
C
N
N
N
S=2
N
H3C
N
N
N
+Br-
Br
N
N
N
N
N
S=0
N
N
N
N
N
N
N
Br
N
N
N
N
N
N
Br
Fe
N
N
N
N
N
N
Fe
Br
N
N
N
N
N
k3
N
N
N
-Br-
N
N
N
Fe
N
N
N
N
Fe
N
N
N
N
-
N
N
S=2
The mechanism was calculated using DFT theory. Each step has been fully optimized
and plotted in Figure 4.8. When the bromide ion was placed next to the iron complex, the
structure optimized with bromide ion 4.594 Å from the iron atom. The thiocyanate and chloride
ions optimized at 4.417 and 4.320 Å, respectively.
The proposed spin state changes were also pursued by calculations. In the preassociation
step, the quintet state energy was ~ 4 eV higher in energy than the singlet state favoring the
singlet state for this species. In the substitution step, calculations indicate that the high spin state
is ~50 kJ/mol lower in energy than the singlet state. To cross the barrier, the reactants pass over
a singlet state transition state with the activation energy listed in Table 4.3. After crossing the
barrier, the spin state change occurs and the subsequent steps occur rapidly. The calculations
support this with another 3 eV drop in energy upon the interaction of a second bromide ion. The
last two steps show a leveling off and an increase in energy, where solvation occurs.
83
N
2
N
N
N
N
N
Fe
N
N
0
N
N
N
N
N
N
N
N
N
N
-2
Fe
N
Br
N
N
N
N
N
N
N
N
N
N
N
N
N
84
Energy (eV)
Br
Br
N
-4
Fe
N
Ki
N
N
N
Fe
N
N
N
N
N
N
N
N
N
N
k3
-6
-6.167 eV
-595.1 kJ mol-1
N
-5.534 eV
-533.9 kJ mol-1
N
Br
N
N
N
N
H3C
N
N
Br
-6.038 eV
-582.6 kJ mol-1
N
Fe
C
N
N
N
N
N
N
Fe
C
N
-8
N
N
C
H3C
N
N
Br
Fe
N
Br
Br
N
Br
N
N
N
CH3
C
N
N
N
CH3
N
-10
-9.608 eV
-927.1 kJ mol-1
-9.610 eV
-927.2 kJ mol-1
-12
Figure 4.8. DFT calculated mechanism for the reaction of Fe(bpz)32+ with an anion
84
-9.142 eV
-882.1 kJ mol-1
4.4. Conclusion
In this paper the decomposition reaction of the cation iron(II)-tris-2,2’-bipyrazine was
studied with different anions. Both experimental and computational studies suggest that the
mechanism involves a spin state change causing complete loss of coordinate bipyrazine ligand.
This mechanism provides new insight into the reaction and may help to explain how the other
iron complexes undergo the same decomposition reaction.
85
CHAPTER 5
COMPUTATIONAL STUDY OF IRON(II) SYSTEMS CONTAINING THE LIGANDS
WITH NITROGEN HETEROCYCLIC GROUPS.
5.1. Computational Technique
The geometries of the complexes 1 – 4 (Figure 5.1) were optimized in the singlet ground
state in the gas phase using the Becke's three-parameter hybrid functional B3LYP154a with the
non-local term of Lee, Yang, and Parr 154b and the local term of Vosko, Wilk, and Nassiar 154c
functional of the Gaussian ’03 program package153. The Stuttgart-Dresden (SDD)154d ECP was
utilized for all the atoms in the molecule.
TDDFT156 calculations were employed to produce a number of singlet excited-states of
the complex ions based on their singlet ground-state optimized geometry in the gas phase. The
output contained information for the excited state energies, oscillator strengths (f) and a list of
the transitions that give rise to each excited state. The orbitals involved as well as the orbital
contribution coefficients of the transitions were obtained. All transitions with f > 0.0000 were
considered to search for the possibility of d-d transitions. GaussSum176 was used to generate both
simulated spectra and orbital information. The molar absorptivity was calculated with a fullwidth-at-half-maximum of 3,000 cm-1.
86
N
2+
2+
N
N
N
N
N
N
N
N
Fe
Fe
N
N
N
N
N
N
N
N
N
Fe(bpy)32+ (1)
Fe(bpz)3
2+
(2)
2+
2+
N
N
N
N
N
N
Fe
Fe
N
N
N
N
N
N
Fe(phen)32+ (3)
Fe(tpy)32+ (4)
Figure 5.1. Schematic drawing of complexes; 1: Fe(bpy)32+; 2: Fe(bpz)32+; 3: Fe(phen)32+; 4:
Fe(tpy)22+
87
5.2. Geometry Optimization
All optimized calculated structures have been compared to crystal structures. The bond
distances between the Fe atoms and the nitrogen atoms are listed in Table 5.1. All of the crystals
used for comparison had the same counter ion as to avoid any anomalies in the packing. The
average difference for all the bond lengths was 0.042 ± 0.012 Å (24 values) longer than the
experimental values.
The B3LYP/6-311G(d) and UB3LYP/6-311G(d,p) basis sets were
compared for complex 2 but no appreciable difference was found, so the B3LYP/SDD basis set
was used for all calculations.
The structures of all the complexes contain two shorter axial bound nitrogen atoms than
the ones in the equatorial position. The calculations mimic this effect but with very little change
between the axial and equitorial distances. These complexes are like most tris chealated metal
complexes which have a D3h, “propeller”, geometry.
88
Table 5.1. Experimental vs. Calculated Bond Distances (Å)
Fe-N
Fe-N
Fe-N
Fe-N
Fe-N
Fe-N
Average
Average
Diff.
Fe(bpy)32+
Exp.177 Calc.
1.947
2.009
1.949
2.009
1.953
2.010
1.961
2.010
1.964
2.010
1.964
2.010
1.956
2.010
Fe(bpz)32+
Exp.137 Calc.
1.953
2.007
1.957
2.007
1.961
2.008
1.966
2.008
1.966
2.008
1.967
2.008
1.962
2.008
Fe(phen)32+
Exp.178 Calc.
1.966
2.017
1.973
2.018
1.980
2.018
1.981
2.019
1.984
2.019
1.984
2.019
1.978
2.018
Fe(tpy)22+
Exp.179 Calc.
1.890
1.913
1.891
1.913
1.978
2.019
1.984
2.019
1.988
2.020
2.001
2.020
1.955
1.984
0.054
0.046
0.040
0.029
5.3. Molecular Orbitals
The molecular orbital diagrams in Figure 5.2 show the electron density distribution in the
HOMO and LUMO orbitals. The data for the composition of the HOMO, LUMO, LUMO+1 and
LUMO+2 are listed in Table 5.2. For the compounds 1 – 3, ~87% of the electron density in the
HOMO is located on the metal and 4% is distributed on each of the three ligands. Compound 4
has less electron density located on the metal (78%) and 11% located on each of the two ligands.
As shown in Figure 5.2, electron density in the LUMO orbitals is primarily located on the
ligands, but not symmetrically as found for ruthenium(II) analogues. 46 For compounds 1 – 3,
~53% lies on one ligand, ~40% on another and the remaining electron density is distributed on
the metal and the third ligand. For compound 4, 81% of the electron density is located on one
ligand, 15% on the other and 4% on the metal. The electron density in the LUMO+1 for
89
Figure 5.2. Molecular orbital diagrams for the optimized structure, HOMO and LUMO orbitals;
1: Fe(bpy)32+; 2: Fe(bpz)32+; 3: Fe(phen)32+; 4: Fe(tpy)22+
90
compounds 1 – 3 follows a similar pattern as in the LUMO. In this case, ~61% of the electron
density resides on one ligand, ~24% on another and the remainder on the third ligand and the
metal. The electron density distribution in LUMO+1 for compound 4 is the same as the LUMO.
Only in LUMO+2 is the electron density evenly distributed among the ligands with no electron
density placed on the iron atom.
Table 5.2. Detailed HOMO, LUMO, LUMO+1, LUMO+2 Electron Density Distributiona
Compoundb HOMO
LUMO
%M
%L
%L
%L
%M
%L
%L
%L
1
88
4
4
4
4
1
54
41
2
87
4
5
4
5
2
53
40
3
86
4
5
5
4
4
52
40
4
15
81
78
11
11
2+
82
6
6
6
1
33
33
33
2+
82
6
6
6
1
33
33
33
4
Ru(bpy)3
Ru(bpz)3
Compound
LUMO+1
LUMO+2
%M
%L
%L
%L
%M
%L
%L
%L
1
4
12
23
61
0
35
34
31
2
5
10
24
61
0
34
33
33
3
4
12
24
60
0
34
32
34
0
51
49
4
15
81
2+
6
7
27
60
6
3
36
55
2+
8
12
19
61
8
1
42
50
4
Ru(bpy)3
Ru(bpz)3
a: Ligands are arbitrary, the percentages organized by increasing number, b: 1: Fe(bpy)32+; 2:
Fe(bpz)32+; 3: Fe(phen)32+; 4: Fe(tpy)22+;
91
5.4. Orbital Energy Levels
Figure 5.3 shows the energies of the 12 frontier orbitals for each of the complexes. The
complexes show a similar orbital distribution within the occupied and virtual orbital energy
levels. In all cases the HOMO, HOMO-1 and HOMO-2 orbital energies are iron centered; all of
the other orbital energies are ligand centered. The complexes have similar energy gaps, but the
HOMO and LUMO orbitals of Fe(bpz)32+ are lower in energy than those of the others.
The energies of the orbitals for complexes 1, 3 and 4 are similar since the ligands have
similar π structures. The LUMO orbitals of the phenanthroline ring are slightly higher in energy
but their spacing is much smaller than for the bipyridine ring. Similarly, the energy level of the
HOMO orbital of phenanthroline complex is higher than that of the bipyridine analogue. In the
terpyridine system, both the HOMO and LUMO orbitals are lower in energy than in the
bipyridine complex; the LUMO orbital energies have a greater decrease in energy than the
HOMO orbitals.
92
-50
L+4
L+4,5
L+5
L+3
-60
L+4
L
L
L+2
L+2,3
L+5
L+1
L+1
L+2,3
L
L+1
-70
L
3
Energy, x 10 cm
-1
L+3,4,5
L+2
L+1
Gap = 30.57
Gap = 29.92
Gap = 29.04
-80
Gap = 30.65
-90
H-2
H
H-2
H-4
H-5
H
H-2
H-5
-100
H-1
H-1
H-4
H
H-3
H-3,4
H-3
H-2
H
H-1
H-5
H-3
H-4
H-5
-110
1
2
3
Complex
4
Figure 5.3. Six occupied and six virtual frontier orbitals; 1: Fe(bpy)32+; 2: Fe(bpz)32+; 3:
Fe(phen)32+; 4: Fe(tpy)22+
93
H-1
5.5. Discussion
5.5.1. Electrochemical Behavior
Electrochemical data and Mulliken charges obtained from the computational studies are
listed in Table 5.3. Complexes 1-3 have three reversible reductions and one reversible oxidation;
complex 4 has only two reversible reductions and one reversible oxidation as reported 139. Linear
correlations between the first reduction potential and the energy of the LUMO for a series of
ruthenium(II) diimine complexes have been reported in the past. 46 Here the energy of the
LUMO also correlates with the first reduction potential of the iron(II) complexes with a slope of
-0.399 ± 0.006 (R2 = 1.00 ± 0.01) as shown in Figure 5.4. Similarly, the energy of the HOMO
for the four complexes also correlates with their oxidation potentials. The graph in Figure 5.4 is
linear with a slope of -0.358 ± 0.004 (R2 = 1.00 ± 0.01). While the plots are linear, additional
points at intermediate potentials would be desirable to substantiate the observed trends.
94
-0.27
-0.41
3
-0.28
4
-0.43
-0.29
-0.44
-0.30
ELUMO, eV
EHOMO, eV
-0.42
3
1
-0.45
-0.32
-0.47
-0.33
2
95
0.8
1.0
1.2
1.4
1.6
4
-0.31
-0.46
-0.48
1
2
-0.34
1.8
-1.6
,V
1/2(ox)
Figure 5.4. Left: Plot of HOMOEenergy
vs. oxidation potential
1: Fe(bpy)32+; 2: Fe(bpz)32+; 3: Fe(phen)32+; 4: Fe(tpy)22+
95
-1.4
-1.2
-1.0
-0.8
-0.6
E1/2(red), V st
Right: Plot of LUMO energy
vs. 1 reduction potential;
Table 5.3. Electrochemical Data and Mulliken Charges
Complexa
Oxidatione
Reductionse
E1/2
E1/2(1)
E1/2(2)
E1/2(3)
1
0.80
-1.54
-1.72
-1.90
1.016
2
1.70
-0.76
-0.92
-1.20
1.073
0.79
-1.57
-1.76
-1.85
1.014
b
b
3
4b
0.90
-1.48
-1.66
2+ c
1.27
-1.31
-1.50
-1.77
1.117
2+ c
1.98
-0.68
-0.87
-1.14
1.233
Ru(bpy)3
Ru(bpz)3
M.C.d
1.107
a: 1: Fe(bpy)32+; 2: Fe(bpz)32+; 3: Fe(phen)32+; 4: Fe(tpy)22+; b: Ref. 138; c: Ref. 148; d Mulliken
Charge; e: Values in volts, scan speed is 100 mV s -1, electrolyte is 0.1 M TBAPF6 in acetonitrile
5.5.2. Energy Levels
The electrochemical potential trends indicate electron density changes occur in the
molecular orbitals of the complexes altering their energy levels. The most difficult complex to
oxidize and easiest to reduce, complex 2, has the lowest energy HOMO and LUMO, as well as
the highest Mulliken charge. This is consistent with the greater electron withdrawal power of the
bipyrazine ligand rendering the iron(II) center more positive than the other two. In like manner,
the slightly less positive charge on the iron(II) center for the phenanthroline derivative compared
to that of the bipyridine analogue is consistent with less electron density being withdrawn from
the iron(II) center when phenanthroline is coordinated. The iron(II) terpyridine complex has a
high Mulliken charge and clearly does not follow the rational discussed for the other three
complexes. This is due to geometry factors related to the tridentate-terpyridine ligand.
The splitting and spacing patterns of the LUMO orbitals is different for complex 1 and 3.
The pattern of the first three orbitals (L, L+1, L+2) is similar, but the next three have a much
larger spacing. The energy gap from the orbitals labeled L+2 to L+3 increases in energy from
96
complex 3 to 1. This is most likely related to the greater aromaticity of the phenanthroline
ligand.
5.5.3. Singlet Excited States and UV-Vis Absorption Spectra
The singlet excited-state spectra were calculated and are displayed in Figure 5.5; the
calculated and experimental transition energies along with assignments are tabulated in Table
5.4. The electronic transitions corresponding to excitation from one electronic level to another
are composed of several, often commensurable orbital-to-orbital transitions represented by the
vertical lines underneath the spectral envelopes. A complete list of the assignments can be found
in the supplementary information found in the APPENDIX D.
Iron(II) differs from most other transition metal complexes studied using DFT and TDDFT
calculations. First, it is a 3d transition element and so d-d transitions are expected due to low
lying d orbitals. Second, the complexes have residual paramagnetism. For example, complex 1
has a magnetic moment of ~1 BM180; complex 2 has a one of 0.7 BM137.
97
Table 5.4. Tabulated data for the experimental and calculated spectra
Complex
EExpa(ε,M-1cm-1)b
Ecalca,c
Assignment
Fe(bpy)32+
32.9(58,000)
19.2 (11,200)
36.7
23.6
π  π*
MLCT
Fe(bpz)32+
32.7 (55,000)
18.2 (12,300)
35.6
24.4
π  π*
MLCT
Fe(phen)32+
23.0 (7,300)
19.4 (11,200)
26.5
24.8
MLCT
MLCT
Fe(tpy)22+
36.5 (40,500)
40.0
π  π*
31.4 (38,000)
33.4
17.8 (12,000)
24.0
3
-1
a: values in x10 cm ;b: in DMF; c: in gas phase
π  π*
MLCT
98
80000
MLCT
d-d
ILCT (π→π*)
80000
70000
-1
60000
Ex. Co., M cm
50000
-1
-1
Ex. Co., M cm
-1
60000
40000
30000
40000
20000
20000
10000
0
45000
0
40000
35000
30000
25000
Wavenumber, cm
20000
45000
40000
-1
35000
30000
Wavenumber, cm
120000
50000
100000
20000
-1
80000
-1
Ex. Co., M cm
40000
-1
Ex. Co., M cm
-1
99
60000
25000
-1
30000
20000
40000
10000
20000
0
45000
60000
0
40000
35000
30000
Wavenumber, cm
25000
20000
45000
-1
40000
35000
30000
Wavenumber, cm
25000
20000
-1
Figure 5.5. Singlet excited state spectra with transitions shown as vertical bars; Top left: Fe(bpy)32+; top right: Fe(bpz)32+; bottom left:
Fe(phen)32+; bottom right: Fe(tpy)22+
99
Electronic d-d transitions have low absorption coefficients; therefore in the calculated
spectra these would have low oscillator strengths. Examination of the time-dependent density
functional theory data related to d-d transitions is tabulated in Table 5.5.
There are d-d
transitions scattered throughout the spectra and are buried under more intense transitions. Each
complex has about two or three d-d transitions located at lower energy than the MLCT bands.
They are not pure d-d transitions, but a good percentage of the transition is d-d, generally greater
than 80%. The calculated extinction coefficients of these transitions are very small to moderate
(~50 - ~300 M-1 cm-1), as would be expected.
Table 5.5. Calculated d-d Transitions (cm-1) and Absorption Coefficients (M-1cm-1)
Complexa 1
Energy
19089
b
Ex. Co.
46.3
2
19322
46.3
3
18856
15.4
4
21424
23.1
Energy
Ex. Co.b
19097
46.3
19328
46.3
18864
23.1
21436
23.1
Energy
Ex. Co.b
28142
239.2
28533
362.7
28309
185.2
28583
0
Ru(bpy)32+ Ru(bpz)32+
31728
547.8
32091
208.3
Energy
28149
28540
28315
28607
31738
32109
b
Ex. Co.
246.9
362.7
185.2
0
509.3
177.5
2+
2+
2+
2+
a: 1: Fe(bpy)3 ; 2: Fe(bpz)3 ; 3: Fe(phen)3 ; 4: Fe(tpy)2 ; b: Reference 181, using a fwmh of
3000 cm-1
Generally for each complex the π  π* transitions occur at high energy (30,000 – 45,000
cm-1) and are ligand centered (LC). The peak ~ 24,000 cm-1 is assigned as mostly metal-toligand charge transfer (MLCT). The calculated absorption maxima are blue-shifted from the
experimental maxima ~3,000 cm-1 for the LC transitions and ~4,000 cm-1 – 5000 cm-1 for the
MLCT transitions. Each of the basis sets mentioned in the geometry optimization section were
100
tried to find a solution to this, but all gave similar results. While this red-shift has often been
found for other metal complexes and corrected by incorporating solvent into the calculation 181, in
these systems only small red-shifts were found when solvent is introduced into the calculations.
A method used to correct the calculated energy maxima using a correlation between
experimental MLCT maxima and calculated maxima as previously reported 169 was also
unsuccessful. There was no correlation found with the MLCT transitions.
The disagreement with experimental spectra may be due to residual paramagnetism of the
complex. This is quite large for a low spin “diamagnetic” iron center, but there are many other
examples of this phenomenon180. To investigate this further and allow for the spin anisotropy,
the unrestricted UB3LYP/6-311g(d,p) basis set was chosen. Yet again all three of the basis sets,
B3LYP/6-311G(d), UB3LYP/6-311G(d,p) and B3LYP/SDD yielded a S2 value of 0.000 for all
complexes.
The experimental transitions are located on a Tanabe-Sugano diagram approximately
near the spin crossover line. The calculated transitions reside well within the low spin region of
the diagram. Thus, the theory or basis sets appear, at this time, unable to effectively treat data
effectively under these conditions.
5.5.4. Comparison to Ru(II)
Ruthenium tris-2,2’-bipyridine has been treated by similar computational methods as
described for the iron complexes. The HOMO orbital for all four iron complexes and the
ruthenium complex shows that ~85 % of the electron density resides on the metal center; the
other 15% is distributed equally among the ligands. On the other hand the LUMO orbital of
Ru(bpy)32+ shows the ligands equally share the distributed electron density unlike the iron
complexes where there is an unequal distribution of electron density. For complexes 1 – 3, two
101
ligands have ~90% of the electron density and the remaining ligand has less than 5%. For
complex 4 one terpyridine ring has 81% and the other has only 15% electron density. For the
LUMO+1 orbital, the electron density is unequally distributed for both the iron and ruthenium
complexes. The opposite result of the LUMO orbital is found for the LUMO+2 orbital. The iron
complexes have an equal distribution of electron density whereas the ruthenium complexes have
an unequal distribution.
In the iron complexes the LUMO and LUMO+1orbitals are degenerate and the LUMO+2
orbitals are 0.01, 0.05, 0.04 and 0.16 eV higher in energy for compounds 1 – 4, respectively.
The LUMO+1 and +2 are higher in energy than the LUMO by 0.13 eV and 0.16 eV for
Ru(bpy)32+ and Ru(bpz)32+, respectively. The energy of the LUMO for Ru(bpy) 32+ is 0.082 eV
higher than for Fe(bpy)32+.
The energy of the HOMO orbitals is dependent on their Mulliken charges.
For
Ru(bpy)32+ the Mulliken charge is more positive than for Fe(bpy)32+, hence its HOMO is lower in
energy. The iron atom is smaller and the dπ orbitals have poorer overlap with the π* levels of
the bipyridine ligands resulting in the less positive Mulliken charge.
5.5.5. Chemical Behavior
Iron complexes have been known for many years to undergo rather rapid ligand
substitution reactions and to have a very strong attraction to certain anions such as chloride,
bromide and thiocyanate, which have all been shown to cause dissociation reactions125-136. Such
reactions are accelerated in the presence of light. Ruthenium complexes, on the other hand, are
stable under most conditions but do undergo slow photosubstition in the presence of excess
halide168. Lability of transition metal complexes has long been attributed to paramagnetism and
102
to population of dζ* states which perturb the bonding interaction. The thermal reaction of iron
complexes in the dark is attributed to residual paramagnetism.
The dd transitions in the iron complexes found by TDDFT calculations would allow light
to populate the dζ* states rendering the complexes labile. The TDDFT calculation in the case of
Ru(bpy)32+ does not result in predicted dd transitions at similarly low energy as found in the iron
complexes. Hence, the ruthenium(II) diimine complexes are more stable to photosubstitution
reactions. Ruthenium(II) complexes also do not have residual paramagnetism; hence, they are
much more thermally stable than their iron(II) analogues.
5.6. Conclusions
A general computational study has been completed on four different but similar iron(II)
diimine complexes. This paper brings to light the difference in the molecular orbital behavior,
but shows how the complexes overall behave as other diimine metal complexes. We hope this
investigation will encourage others to begin an in depth investigation into a theoretical basis for
treating systems with residual paramagnetism.
103
CHAPTER 6
CRYSTAL STRUCTURE REPORTS
6.1 fac-Bipyrazyltricarbonyl(aquo)rhenium(I) hexafluorophosphate dehydrate
6.1.1. Experimental
Re(CO)5Cl and AgTRIF (1:1) were combined in ethanol and refluxed overnight in the
dark. The AgCl was removed by filtration. Then 1 eq. of 2,2'-bipyrazine was added and the
mixture was refluxed for one hour. Next, 1 eq. of pyridine was added and the mixture was
refluxed overnight. The solvent volume was reduced and then added to an aqueous saturated
NH4PF6 solution. The solid that formed was filtered immediately, washed with ether, and dried.
(Yield= 65%) Crystals were obtained from an ethanol/water mixture. The solution was left on
the counter for the ethanol to evaporate. While standing, water substituted for the pyridine and
the title compound was obtained. Schematic drawing of resulting compound shown in Figure 6.1.
104
Figure 6.1. Schematic drawing of Re(CO)3(bpz)(H2O).PF6.2H2O
6.1.2. X-Ray Analysis and Refinement
Data collection: Bruker Kappa APEX II160; cell refinement: Bruker Kappa APEX II160;
data reduction: Bruker SAINT160; program(s) used to solve structure: Bruker SHELXTL160;
program(s) used to refine structure: SHELXL97160; molecular graphics: Bruker SHELXTL160;
software used to prepare material for publication: Bruker SHELXTL.
Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are
based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The
threshold expression of F2 > 2sigma(F2) is used only for calculating R-factors(gt) etc. and is not
relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about
twice as large as those based on F, and R-factors based on ALL data will be even larger.
All non-hydrogen atoms were refined using anisotropic thermal parameters. Hydrogen
atoms on the water molecules were found on the fourier map and their positional parameters
were fixed. All other hydrogen atoms were included at idealized positions and were not refined.
105
The compound sits on a mirror plane in the orthorhombic space group Pcmn. Both the cation and
anion are bisected by a mirror plane of symmetry. The (PF6)- anion was modeled for a rotational
disorder (50/50) along the F(1)—P(1)—F(2) axis with anisotropic treatment of the disordered
fluorine atoms. Crystal structure data and refinement details are in Table 6.1 and ORTEP
drawing in Figure 6.2. Full data shown in APPENDIX E.
106
Table 6.1. Crystal Structure Data and Refinement
Identification code
RK005
Empirical formula
C11H11N4O6F6PRe
Formula weight
Temperature
Wavelength
Crystal system
Space group
626.41
298 K
0.71073 Ǻ
Orthorhombic
Pcmn
Unit cell dimensions
a = 8.998(4) Ǻ
b = 13.065(6) Å
c = 15.511(3) Å
α = 90°
Volume
Z
Calculated density
β = 90°
γ = 90°
1823.5(12) Å3
4
2.282 g/cm3
Absorption coefficient
F(000)
Crystal size
Crystal habit
6.850 mm-1
1188
0.4 x 0.3 x 0.1 mm
Needle
Crystal color
Orange
2.62 to 24.99o
0≤ h ≤ 10
0 ≤ k ≤ 15
0 ≤ l ≤ 18
1680 [R(int) = 0.0000]
 range for data collection
Limiting indices
Reflections collected / unique
Completeness to  = 24.98
Refinement method
Data / restraints / parameters
Refinement threshold
99.8 %
Full-matrix least-squares on F2
1680 / 5 / 174
Final R indices [I>2(I)]
R indices (all data)
I>2(I)
1967
1.058
R1 = 0.0261, wR2 = 0.0633
R1 = 0.0391, wR2 = 0.0654
Largest diff. peak and hole
0.866 and -0.873 e.A-3
Data > threshold
Goodness-of-fit on F2
107
Figure 6.2. ORTEP drawing with 50% probability161
6.1.3. Comment
During recrystallization of [Re(CO)3(Bpz)(py)](PF6), a light induced reaction took place
producing I. Pyridine was replaced by a water molecule(1). The cation (Figure 6.1 and Table 6.1)
shows a distorted octahedal geometry defined by two N and one O donors and three carbonyl
ligands that are arranged so that a fac-isomer is formed. A comparison of bond lengths, all in
angstroms, to two similiar complexes having 2,2'-bipyridine (2) and 1,10-phenanthroline (3)182
bound in place of 2,2'-bipyrazine (1) reveal that the Re---L bond lengths, where L is the ligand
attached, are virtually identical: (1) = 2.161, 2.161; (2) = 2.161, 2.165; (3) = 2.161, 2.183. The
Re---CO bond distances in the equatorial position are: (1) = 1.913, 1.913; (2) = 1.914, 1.901; (3)
108
= 1.938, 1.931 and in the axial position compare as follows: (1) = 1.888; (2) = 1.882; (3) = 1.898.
The most interesting part of the title complex is the water molecule bound in the axial position.
The Re-O bond distances, table 6.2, show how the bipyridine and phenanthroline rings dontate
electron density producing a larger bond distance. When the bipyrazine is present there is a
withdrawing effect on the rhenium center causing the bond to be shorter. The same effect is
carried through the bond distances seen between the oxygen atom bound to rhenium and the
oxygen atom that is hydrogen bound. The bipyrazine group produced a bond that was shorter
when compared to the bipyridine containing complex. This again shows the effect of the ring
system not only on the inner sphere environment but also the outer sphere environment.
Table 6.2. Rhenium-Oxygen and Oxygen-Oxygen bond distances (Å)
Re - Ox Ox - Ox
(1) 2.146
2.596
(2) 2.190
2.623
(3) 2.181
NA
109
6.2. 4b,5,7,7a-tetrahydro-4b,7a-epiminomethanoimino-6H-imidazo[4,5-f]
[1,10]phenanthroline-6,13-dione monohydrate
6.2.1. Experimental
1,10-phenanthroline-5,6-dione was prepared. Urea was purchased from Aldrich and used
as received. Toluene and glacial acetic acid were purchased from Fisher Scientific Company and
used as received. 200 proof ethanol was purchased from AAPER alcohol and used without
further purification.
The title molecule, shown in Figure 6.3, was prepared and purified as previously
reported. Crystals were obtained by refluxing the title molecule in glacial acetic acid and then
allowing the solution to cool. Crystals suitable for X-Ray analysis formed on the bottom of the
flask. Elemental Anyalysis: Anal. For C14H10N6O2.2H2O: %C, 50.90; %H, 4.24; %N, 25.45;
Found. %C, 50.90; %H, 3.60; %N, 24.77.
Physical Measurements: Fluorescence measurements were obtained with a Spex
Fluorolog 2:1:2 spectrophotometer. The crystals were placed between two glass slides and then
lined up within the excitation chamber using a mount. The slit widths were maintained at 1.4 mm
and the light intensity collected with a Hamamatsu R928 photomultiplier tube with a 900 V bias.
Data was gathered at intervals of 0.1 nanometers and integrated for 0.1 seconds. The data was
processed using the Origin 6.1 suite of software and massaged to give smoother spectra without
loss of spectral features.
110
Figure 6.3. Schematic drawing of 4b,5,7,7a-tetrahydro-4b,7a-epiminomethanoimino-6Himidazo[4,5-f][1,10]phenanthroline-6,13-dione monohydrate
6.2.2. X-Ray Analysis and Refinement
Data collection: Bruker Kappa-Apex II160; cell refinement: Bruker Kappa Apex II160;
data reduction: Bruker SAINT160; program(s) used to solve structure: Bruker SHELXTL160;
program(s) used to refine structure: SHELXL97160; molecular graphics: Bruker SHELXTL160;
software used to prepare material for publication: Bruker SHELXTL.
Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of
fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2.
The threshold expression of F2 > 2sigma(F2) is used only for calculating R-factors(gt) etc. and is
111
not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically
about twice as large as those based on F, and R- factors based on ALL data will be even larger.
All non-hydrogen atoms were refined using anisotropic thermal parameters. Hydrogen atoms on
the solvate water molecule and urea nitrogen atoms were refined using isotropic thermal
parameters. All other hydrogen atoms were included at idealized positions and not refined.
Crystal structure data and refinement details are in Table 6.3 and ORTEP drawing in Figure 6.4.
Full data shown in APPENDIX E.
112
Table 6.3. Crystal Structure Data and Refinement
Identification code
RK0026
Empirical formula
C14H10N6O • H2O
Formula weight
Temperature
Wavelength
Crystal system
Space group
312.30
150 K
0.71073 Ǻ
Monoclinic
P21/c
Unit cell dimensions
a = 18.5164(18) Å
b = 12.3920(12) Å
c = 12.6929(13) Å
α = 90°
Volume
Z
Calculated density
β = 108.528(5)°
γ = 90°
2761.5(5) Å3
8
1.502 g/cm3
Absorption coefficient
F(000)
Crystal size
Crystal habit
0.111 mm-1
1296
0.49 x 0.30 x 0.25 mm
Block
Crystal color
Lustrous Grey
3.44 to 26.00o
-22 ≤ h ≤ 22
-15 ≤ k ≤ 15
-15 ≤ l ≤ 15
68322 [R(int) = 0.0316]
 range for data collection
Limiting indices
Reflections collected / unique
Completeness to  = 26.00
Refinement method
Data / restraints / parameters
Refinement threshold
99.8 %
Full-matrix least-squares on F2
5422 / 0 / 451
Final R indices [I>2(I)]
R indices (all data)
I>2(I)
4600
1.033
R1 = 0.0357, wR2 = 0.0859
R1 = 0.0444, wR2 = 0.0922
Largest diff. peak and hole
0.510 and -0.266 e.A-3
Data > threshold
Goodness-of-fit on F2
113
Figure 6.4. ORTEP drawing with 50% probability161
6.2.3. Comment
The title compound has been snythesized before and included in many different metal
systems as a ligand183-186 . Crystal structures have been solved for the metal complexes which
contain the title compound, but to date the structure of the unbound compound has not been
solved. According to the crystal structure, each molecule forms three hydrogen bonds; one with
another molecule and two with two different water molecules. Each water molecule forms four
hydrogen bonds; two to urea NH groups, one to a urea ketone and one to a bipyridine nitrogen
atom. The bipyridine rings are twisted out of plane which causes the urea groups to also twist.
The hydrogen bonds of interest occur between H12-O1, H3-O2s, and H10-O2s, Table 6.4; these
three bonds form a ring that gives stability to the molecule in the packing arrangement. The
hydrogen bonds are consistent with the average reported value of 2.0 Å.187
Photophysical Processes: The emission spectra and excitation spectra were determined in
the solid state. The excitation spectra shows one major transition at 375 nm and is assigned to a
114
π→π* transition within the bipyridine moiety. The emission spectra and excitation spectra have
good overlap. The emission spectrum reveals very nice vibrational structure. The three major
peaks are located at 405, 426, and 453 nm. The vibrational band spacing was found to be 1300
cm-1.
Table 6.4. Hydrogen bonds distances (Å) and angles (◦)
Donor-H···Acceptor N-H
D···A (Å) H···A (Å) <D-H···A (°)
N12—H12···O1
0.896 2.726
1.835
172.5
N3—H3···O2s
0.826 2.907
2.082
176.3
N10—H10···O2s
0.860 2.833
1.991
165.9
115
CHAPTER 7
DETERMINATION OF QUANTUM YIELDS: USE OF A STANDARD EQUATION
7.1. Introduction
Emission quantum yields have been determined for many years in solution, the solid state
and glasses ranging in temperature from below 77 K to above 298 K. Theoretically, emission
quantum yields can be determined directly using actinometry to determine the irradiation
intensity188. However, to avoid the time consuming process of actinometry, the ratio method was
developed165, see Equation 7.1.
 I  A    
 L1   L 2  L1  L 2   L1 
 I L 2  AL1    L 2 
2
(7.1)
υL1 and υL2 are the quantum yields for species 1 and 2, IL1 and IL2 are the integrated area under
their emission envelopes, AL1 and AL2 are their absorbances and ηL1 and ηL2 are the indices of
refraction of their solvents, eq. 7.1 has most often been used to deduce emission quantum yields
relative to a standard (species 2). While this method has been used for solution measurements, it
has not been applied as extensively to glasses at 77 K, particularly for inorganic complexes due
to experimental difficulties. There are also several potential errors that can arise if one does not
know how to use the equation properly. If solvent refraction indices are not taken into account
then the numbers obtained would be irrelevant. Literature examples of this type of error are hard
to find, because these errors are generally propagated through several papers. Here, we report a
procedure to determine emission quantum yields based on a linear correlation. The correlation
removes the need for solvent corrections and allows for different temperatures to be explored.
116
7.2. Materials and Methods
Solvents used for emission studies were 4:1 ethanol:methanol, propylene carbonate and
n-butyronitrile. The ethanol was absolute (AAPER Alcohol) and the methanol was reagent grade
(Fisher). Propylene carbonate and n-butyronitrile were obtained from Aldrich; n-butyronitrile
was distilled prior to use.
Ruthenium tris-2,2’-bipyridine (bpy) hexafluorophosphate189,
ruthenium tris-1,10-phenanthroline (phen) hexafluorophosphate190 and ruthenium bis-2,2’bipyridine dicyanide191 were synthesized by literature methods. Rhodamine 6G and Rhodamine
B were purchased from Baker, TM Grade, and Matheson, Coleman & Bell, respectively, and
used without further purification.
7.3. Instrumentation
A HP8452 Diode Array Spectrophotometer was used to determine the absorbance of the
solution.
The concentration of the photochromophore was adjusted by dilution until the
absorbance was ~0.1 in a 1 cm cell. A Spex Fluorolog 212 spectrofluorometer was used to
record the emission spectra. A 450 watt xenon arc lamp powered by an external power supply
was used. The intensity of the lamp does change somewhat over the wavelength region of the
measurements from 400 – 520 nm. All four slits were set to 1.4 mm and a R928 Hamamatsu
photomultiplier tube was used as the detector. Spectra were recorded from 500 nm to 850 nm.
The area under the emission curve was determined by integration using the Origin program
suite192.
7.4. Experimental Procedure
Square, quartz cells (1cm) were used at 298 K and round 10 mm (OD) tubes were use at
77 K. The square, quartz cells as shown in Figure 7.1 consisted of a round-bottom degassing
117
chamber, a 1 cm square cuvette and a 10 mm (OD) tube on the top. The round tubes (0.79
mmID) for 77 K measurements were fabricated from pyrex on the top and quartz on the bottom
where excitation occurred193. (The cell path lengths are needed for absorbances.) Samples were
then dissolved in their respective solvents with their excitation wavelength absorbance set to ~
0.1 in a 1 cm cell and these solutions were then introduced into the sample cells so the depth of
the solution was ~ 3 cm. NMR sealing manifolds were then attached to the 10 mm tubes on the
top of the cells and the solutions were frozen in a dewar filled with liquid N 2. The freeze-thawpump technique was repeated at least three times to remove gas from the solutions. Emission
spectra were then obtained from these evacuated, degassed systems.
118
Figure 7.1. Schematic of Room Temperature Degassing Cell
119
Sample tubes for 77 K measurements were immersed in a quartz finger dewar containing
liquid N2. The dewar was mounted in the center of the sample compartment which was modified
to allow dry N2 gas to flow over the finger of the dewar in order to minimize condensation of
moisture from the air. The sample was held in place by a series of rubber rings located near the
top and middle of the sample tube. This ensured that the tube was centered in all directions.
Accurate results were obtained with the sample centered in the excitation beam and with a frostfree finger. Great efforts were made to ensure the maximum emission intensity was obtained
from the sample.
In order to use this method, instrumentation parameters must be held constant. The slit
widths, the integration time and the resolution must remain the same every time the experiment
is run. For the measurements in this paper, the slit widths were 1.40 mm, the integration time
was 0.10 seconds and the resolution was 0.50 nm. Standards need to be rerun if any of these
parameters is/are changed so that the resulting linear correlation can be changed.
7.5. Results and Discussion
The relationship for emission quantum yields in equation 7.2 was derived by theoretical
treatments and described in Ref. 165.
I
L
I0
1 10 
A
L
(7.2)
In equation 7.2, I0 is the number of photons irradiating the sample,IL is the number of photons
emitted, υL is the emission quantum yield and A is the absorbance of the sample at the excitation
wavelength. When rearranged for the experimentally determined emission quantum yields, it
gives equation 7.3.
120

L

I 1
I
0
L
10
A
(7.3)

Eight standards with known quantum yields were chosen from the literature and their
emission intensities were measured166,189,190. A plot of the reported emission quantum yields vs.
the area under the emission curves divided by the absorbance adjustment yielded a straight line
when the quantum yield was large. As the quantum yield went below 0.1 a deviation developed
which caused the predicted quantum yield to be lower than the reported value. For this reason a
log vs. log plot was generated. This removed the deviation observed at low quantum yields and
yielded a correction factor (κR) with the intercept value as the log I 0. Equation 7.4 shows the
equation and Figure 7.2 shows the plot generated.
log
 
L

  R log  I L
 1  10 A


121


  log
I0


(7.4)
Log (IL / (1-10-A))
6.5
7.0
7.5
8.0
8.5
0.0
9.0
6
log (υL) = 0.910(log (IL/(1-10-A)) - 7.858
R² = 0.999
5
-0.2
-0.4
Log (φL)
4
3
-0.6
-0.8
-1.0
2
-1.2
1
-1.4
Figure 7.2. Plot of selected values; 1: Ru(bpy)32+ in 4:1 EtOH:MeOH at 298K; 2: Ru(bpy)32+ in
propylene carbonate at 298K; 3: Ru(bpy)2(CN)2 in 4:1 EtOH:MeOH at 77K; 4: Ru(bpy)32+ in 4:1
EtOH:MeOH at 77K; Rhodamine B in EtOH at 298K; Rhodamine 6G in water at 298K
122
The correlation factor is 0.999 for all the data. The antilog of the intercept divided by the
slope yields I0 which is 4.42x108 cps, but when actinometry was run on the system the I0 was
found to be 2.74x1010. This is a 60 fold difference in intensity which is accounted for by
considering self-quenching, reflection, refraction, and other instrumentation errors. These errors
are very difficult to measure and quantify.
Table 7.1 lists the compounds, the temperature of the measurement and the solvent used
The emission spectra were examined with our instrument under the specified instrumental
conditions and the emission quantum yields obtained from the linear correlation in Figure 7.2
were in agreement with published information as listed in Table 7.1. The difference for each
measurement was small relative to the size of the quantum yield with the exception of one
sample. The second value in question is the 77K quantum yield for the Ru(phen) 32+, this
difference is believed to stem from the difference in the anion used. The literature value uses a
diiodide salt which when the solution is frozen will form ion pairs. Since iodide is so large the
heavy atom effect takes hold and the emission is quenched. The sample ran for this paper was the
dihexaflourophosphate salt, thus virtually eliminating the heavy ion effect allowing for a more
accurate quantum yield to be determined. Emission quantum yields for [Ru(bpy) 3]2+ were
reported to be solvent dependent.189 The linear curve method removes the need to correct for the
dielectric constant of the solvent and the need to use standards for each different solvent
measured.
123
Table 7.1. Quantum Yield Results
Compound
#a
Temp (K)
Solvent
Lit. υL
Exp. υL
∆
λEx
Ref.
Ru(bpy)32+ b
1
298
4:1
0.064e
0.064
0.000
450
189
Ru(bpy)32+ b
2
298
PCd
0.071
0.069
-0.002
452
189
Ru(bpy)32+ b
298
Water
0.042
0.039
-0.003
454
189
Ru(bpy)32+ b
298
Butyronitrile
0.060
0.051
-0.009
454
189
77
4:1
0.376
0.389
0.013
450
166
Ru(phen)32+
298
4:1
0.0288
0.023
0.005
450
190
Ru(phen)32+ c
77
4:1
0.584
0.819
0.235
450
166
Ru(bpy)2(CN)2c
298
4:1
n.a.
0.023
n.a.
460
Ru(bpy)32+
4
124
Ru(bpy)2(CN)2
3
77
4:1
0.269
0.284
0.015
460
166
Rhodamine B
5
298
Ethanol
0.68
0.669
-0.011
488
194
Rhodamine 6G
6
298
Water
0.95
0.915
-0.035
510
195
Used for standards for graph in figure 4. b. Solvent studies. c. Determined here.
d. propylene carbonate. e. Number obtained by calculating from the acetonitrile sample
124
7.6. Conclusion
In summary, the methods outlined here will allow one to obtain emission quantum yields
from a linear correlation established experimentally for a given set of instrumental conditions in
various solvents and at two different temperatures with consistency. The correlation requires
determining IL for standards, κR for each instrument and that the light intensity of irradiation
remains nearly constant over the wavelengths of excitation. The reported emission quantum
yields of [Ru(bpy)3]2+ in solutions of different solvents varies from 0.04 to 0.09 189. The value
selected for comparison to experimental data is, some cases, chosen without an understanding of
the solvent dependency. We present a more reliable method that also can be used to determine
emission quantum yields over a broad temperature range. The values obtained contain less error
than those reported in the literature where the errors quoted range from 10 to 30166,189.
125
CONCLUDING REMARKS
The scope of the research presented in this thesis shows the diversity and connectivity
within in the field of chemistry. Chapter 2 is a in depth study of a series of rhenium(I) tricarbonyl complexes. It showed that the addition of methyl groups to the bipyrazine ring caused
the ring to behave like a bipyrimidine ring electronically. This work will be continued by
oxidizing the methyl groups to carboxylic acids and synthesizing the ruthenium(II) analogs.
These analogs can then be attached to a TiO2 surface and their usefulness as solar cells can be
tested.
The O-Bpy ligand containing complexes with ruthenium revealed that even if two
ruthenium bipyridine subunits are tethered very close together they will still act independently.
This is an avenue that will be explored for the design of catalysts. One change that will be made
is to remove the two bipyridine rings and substitute a terpyridine ring. This will open up a
coordination sight on both ruthenium centers allowing substrates to interact directly with the
metal center. The major application for investigation is the conversion of water to oxygen.
The investigation into the different iron sytems revealed the lability of the bipyrazine
complex is most likely due to a spin state change after the anions react. The computational study
discovered that the residual magnetic moment present in these systems cannot be accurately
accounted for in calculated absorption spectra. A further investigation into a way to better handle
the magnetic moment is needed. This exsists in other metal complexes and the development of
better theory will help in the understanding of these systems.
126
The ability to calculate quantum yields at different temperatures and in different solvents
opens the door to exploring the changes systems undergo as conditions change. This process of
obtaining quantum yields is fast and convinent, but the number of data points needs to be
expanded to help verify the results. It is the hope that this method will become routine in labs
that do photophysical work.
127
REFERENCES
128
LIST OF REFERENCES
1.
Yanagida, M.; Miyamoto, K.; Sayama, K.; Kasuga, K.; Kurashige, M.; Abe, Y.;
Sugihara, H. Journal of Physical Chemistry C 2007, 111(1), 20
2.
(a) Cazzanti, S.; Caramori, S.; Argazzi, R.; Elliott, C. M.; Bignozzi, C. A. Journal of the
American Chemical Society 2006, 128(31), 9996 (b) Jiang, K.-J.; Masaki, N.; Xia, J.-B.;
Noda, S.; Yanagida, S. Chemical Communications (Cambridge, United Kingdom) 2006,
(23), 2460
3.
Onozawa-Komatsuzaki, N.; Kitao, O.; Yanagida, M.; Himeda, Y.; Sugihara, H.; Kasuga,
K. New Journal of Chemistry 2006, 30(5), 689
4.
Li, X.; Hou, K.; Duan, X.; Li, F.; Huang, C. Inorganic Chemistry Communications 2006,
9(4), 394
5.
Kuang, D.; Ito, S.; Wenger, B.; Klein, C.; Moser, J.-E.; Humphry-Baker, R.;
Zakeeruddin, S. M.; Graetzel, M. Journal of the American Chemical Society 2006,
128(12), 4146
6.
Fukui, A.; Komiya, R.; Yamanaka, R.; Islam, A.; Han, L. Solar Energy Materials &
Solar Cells 2006, 90(5), 649
7.
Bolink, H. J.; Cappelli, L.; Coronado, E.; Graetzel, M.; Nazeeruddin, Md. K. Journal of
the American Chemical Society 2006, 128(1), 46
8.
Nazeeruddin, M. K.; De Angelis, F.; Fantacci, S.; Selloni, A.; Viscardi, G.; Liska, P.; Ito,
S.; Takeru, B.; Graetzel, M. Journal of the American Chemical Society 2005, 127(48),
16835
9.
Ito, S.; Liska, P.; Comte, P.; Charvet, R.; Pechy, P.; Bach, U.; Schmidt-Mende, L.;
Zakeeruddin, S. M.; Kay, A.; Nazeeruddin, M. K.; Graetzel, M. Chemical
Communications (Cambridge, United Kingdom) 2005, (34), 4351
10.
Wang, P.; Wenger, B.; Humphry-Baker, R.; Moser, J.-E.; Teuscher, J.; Kantlehner, W.;
Mezger, J.; Stoyanov, E. V.; Zakeeruddin, S. M.; Graetzel, M. Journal of the American
Chemical Society 2005, 127(18), 6850
11.
Gallagher, L. A.; Serron, S. A.; Wen, X.; Hornstein, B. J.; Dattelbaum, D. M.;
Schoonover, J. R.; Meyer, T. J. Inorganic Chemistry 2005, 44(6), 2089
12.
Kils, K.; Mayo, E. I.; Brunschwig, B. S.; Gray, H. B.; Lewis, N. S.; Winkler, J. R.
Journal of Physical Chemistry B 2004, 108(40), 15640
129
LIST OF REFERENCES (continued)
13.
14.
Song, L. Q.; Ding, H. Y.; Wang, X. S.; Zhang, B. W.; Cao, Y.; Feng, J.; Ai, X. C.;
Zhang, J. P. Journal of Photochemistry and Photobiology, A: Chemistry 2004, 165(1-3),
137
Stergiopoulos, T.; Karakostas, S.; Falaras, P. Journal of Photochemistry and
Photobiology, A: Chemistry 2004, 163(3), 331
15.
Kusama, H.; Arakawa, H. Solar Energy Materials and Solar Cells 2004, 82(3), 457
16.
Moss, J. A.; Yang, J. C.; Stipkala, J. M.; Wen, X.; Bignozzi, C. A.; Meyer, G. J.; Meyer,
T. J. Inorganic Chemistry 2004, 43(5), 1784
17.
Wang, P.; Zakeeruddin, S. M.; Comte, P.; Charvet, R.; Humphry-Baker, R.; Graetzel, M.
Journal of Physical Chemistry B 2003, 107(51), 14336
18.
Nitahara, S.; Terasaki, N.; Akiyama, T.; Yamada, S. Thin Solid Films 2003, 438-439,
230
19.
Nonomura, K.; Yoshida, T.; Schlettwein, D.; Minoura, H. Electrochimica Acta 2003,
48(20-22), 3071
20.
Wang, P.; Zakeeruddin, S. M.; Moser, J. E.; Nazeeruddin, M. K.; Sekiguchi, T.; Graetzel,
M. Nature Materials 2003, 2(6), 402
21.
Kuciauskas, D.; Monat, J. E.; Villahermosa, R.; Gray, H. B.; Lewis, N. S.; McCusker, J.
K. Journal of Physical Chemistry B 2002, 106(36), 9347
22.
Monat, Jeremy E.; Rodriguez, Jorge H.; McCusker, James K. Journal of Physical
Chemistry A 2002, 106(32), 7399
23.
Garcia, C. G.; Nakano, A. K.; Kleverlaan, C. J.; Murakami I., Neyde Y. Journal of
Photochemistry and Photobiology, A: Chemistry 2002, 151(1-3), 165
24.
Anandan, S.; Latha, S.; Maruthamuthu, P. Journal of Photochemistry and Photobiology,
A: Chemistry 2002, 150(1-3), 167
25.
Argazzi, R.; Bignozzi, C. A.; Yang, M.; Hasselmann, G. M.; Meyer, G. J. Nano Letters
2002, 2(6), 625
26.
Kuwahara, Y.; Akiyama, T.; Yamada, S. Langmuir 2001, 17(19), 5714
27.
Ionescu, R. E.; Cosnier, S.; Herzog, G.; Gorgy, K.; Leshem, B.; Herrmann, S.; Marks, R.
S. Enzyme and Microbial Technology 2007, 40(3), 403
130
LIST OF REFERENCES (continued)
28.
Wang, J.; Liu, G.; Lin, Y. Small 2006, 2(10), 1134
29.
Liu, J.; Su, B.; Lagger, G.; Tacchini, P.; Girault, H. H. Analytical Chemistry 2006,
78(19), 6879
30.
Haddour, N.; Chauvin, J.; Gondran, C.; Cosnier, S. Journal of the American Chemical
Society 2006, 128(30), 9693
31.
Bakir, M.; Gyles, C. Journal of Molecular Structure 2005, 753(1-3), 35
32.
Mugweru, A.; Wang, B.; Rusling, J. Analytical Chemistry 2004, 76(18), 5557
33.
Liang, P. Y.; Chang, P. W.; Wang, C. M. Journal of Electroanalytical Chemistry 2003,
560(2), 151
34.
Wang, B.; Rusling, J. F. Analytical Chemistry 2003, 75(16) 4229
35.
Hasegawa, T.; Yonemura, T.; Matsuura, K.; Kobayashi, K. Bioconjugate Chemistry
2003, 14(4), 728
36.
Erdem, A.; Kerman, K.; Meric, B.; Ozkan, D.; Kara, P.; Ozsoz, M. Turkish Journal of
Chemistry 2002, 26(6), 851
37.
Kosela, E.; Elzanowska, H.; Kutner, W. Analytical and Bioanalytical Chemistry 2002,
373(8), 724
38.
Zhang, C.; Haruyama, T.; Kobatake, E.; Aizawa, M. Analytica Chimica Acta 2000,
408(1-2), 225
39.
Yokoyama, K.; Sasaki, S.; Ikebukuro, K.; Takeuchi, T.; Karube, I.; Tokitsu, Y.; Masuda,
Y. Talanta 1994, 41(6), 1035
40.
Ismail, K. Z.; Weber, S. G. Biosensors & Bioelectronics 1991, 6(8), 699
41.
Xu, Z.; Guo, Z.; Dong, S. Biosensors & Bioelectronics 2005, 21(3), 455
42.
Gao, Z.; Tansil, N. C. Nucleic acids research 2005, 33(13), e123
43.
Dennany, L.; Forster, R. J.; White, B.; Smyth, M.; Rusling, J. F. Journal of the American
Chemical Society 2004, 126(28), 8835
44.
Dong, D.; Zheng, D.; Wang, Fu-Q.; Yang, Xi-Q.; Wang, N.; Li, Y.-G.; Guo, L.-H.;
Cheng, J. Analytical chemistry 2004, 76(2), 499
131
LIST OF REFERENCES (continued)
45.
Liang, M.; Guo, L.-H. Environmental Science & Technology 2007, 41(2), 658
46.
Stoyanov, S. R.; Villegas, J. M.; Rillema, D. P. Inorg. Chem. 2002, 41, 2941
47.
Wrighton, M.; Morse, D. L. J. Am. Chem. Soc. 1974, 96, 998
48.
49.
Giordano, P. J.; Wrighton, M. S. J. Am. Chem. Soc. 1979, 101, 2888
Wrighton, M. S.; Geoffroy, G. L. Organometallic Photochemistry; 1979, Academic
Press: New York, Chapter 2.
50.
Lees, A. Chem. Rev. 1987, 87, 711
51.
Giordano, P. J.; Fredericks, S. M.; Wrighton, M. S.; Morse, D. L. J. Am. Chem. Soc.
1978, 100, 2257
52.
Fredericks, S. M.; Luong, J. C.; Wrighton, M. S. J. Am. Chem. Soc. 1979, 27, 7415
53.
Smothers, W. K.; Wrighton, M. S. J. Am. Chem. Soc. 1983, 105, 1067
54.
Vogler, A.; Kisslinger, J. Inorg. Chim. Acta 1986, 115, 193
55.
Juris, A.; Campagna, S.; Bidd, I.; Lehn, J. M.; Zeissel, R. Inorg. Chem. 1988, 27, 4007
56.
Van Wallendael, S.; Shaver, R. J.; Rillema, D. P.; Yoblinski, B. J.; Stathis, M.; Guarr, T.
F. Inorg. Chem. 1990, 29, 1761
57.
Sahai, R.; Rillema, D. P.; Shaver, R. J.; Van Wallendael, S.; Jackman, D. C.; Boldaji, M.
Inorg. Chem. 1989, 28, 1022
58.
Ruminski, R.; Cambron, R. T. Inorg. Chem. 1990, 29, 1574
59.
Baiano, J. A.; Carlson, D. L.; Wolosh, G. M.; DeJesus, D. E.; Knowles, C. F.; Szabo, E.
G.; 14. Murphy, W. R., Jr. Inorg. Chem. 1990, 29, 2327
60.
Tapolsky, G.; Duesing, R.; Meyer, T. J. J. Phys. Chem. 1989, 93, 2885
61.
Tapolsky, G.; Duesing, R.; Meyer, T. J. Inorg. Chem. 1990, 29, 2285
62.
Lin, R.; Guarr, T. F. Inorg. Chim. Acta 1990, 167, 149
63.
Lin, R.; Guarr, T. F.; Duesing, R. Inorg. Chem. 1990, 29, 4169
64.
Kalyasundaram, K. J. Chem. Soc., Faraday Trans. 2 1986, 82, 2401
132
LIST OF REFERENCES (continued)
65.
Sacksteder, L.; Zipp, A. P.; Brown, E. A.; Streich, J.; Demas, J. N.; DeGraff, B. A. Inorg.
Chem. 1990, 29, 4335
66.
Leasure, R. M.; Sacksteder, L.; Nesselrodt, D.; Reitz, G. A.; Demas, J. N.; DeGraff, B. A.
Inorg. Chem. 1991, 30, 3722
67.
Hino, J. K.; Della Ciana, L.; Dressicak, W. J.; Sullivan, B. P. Inorg. Chem. 1992, 31,
1072
Della Ciana, L.; Dressicak, W. J.; Sandrini, D.; Maestri, M.; Ciano, M. Inorg. Chem.
1990, 29, 2792
68.
69.
Meyer, T. J. Pure Appl. Chem. 1986, 58, 1193
70.
Caspar, J. V.; Sullivan, B. P.; Meyer, T. J. Inorg. Chem. 1984, 23, 2098
71.
Kober, E. M.; Marshall, J. L.; Dressick, W. J.; Sullivan, B. P.; Meyer, T. J. Inorg. Chem.
1985, 24, 2755
72.
Lo, K.K.-W.; Hui, W.-K.; Chung, C.-K.; Tsang, K.H.-K.; Lee, T.K.-M.; Li, C.-K.; Lau,
J.S.-Y.; Ng, D.C.-M. Coord. Chem. Reviews 2006, 250, 1724
73.
(a) Di Bilio, A.J.; Crane, B.R.; Wehbi, W.A.; Kiser, C.N.; Abu-Omar, M.M.; Carlos,
R.M.; Richards, J.H.; Winkler, J.R.; Gray, H.B. J. Am. Chem. Soc. 2001, 123, 3181 (b)
Dunn, A.R.; Belliston-Bittner, W.; Winkler, J.R.; Getzoff, E.D.; Stuehr, D.J.; Gray, H.B.
J. Am. Chem. Soc. 2005, 127, 5169 (c) Saidi, M.; Seifert, S.; Kretzschmar, M.;
Bergmann, R.; Pietzsch, H.- J. J. Organomet. Chem. 2004, 689, 4739 (d) Pietzsch, H.-J.;
Gupta, A.; Reisgys, M.; Drews, A.; Seifert, S.; Syhre, R.; Spies, H.; Alberto, R.; Abram,
U.; Schubiger, P.A.; Johannsen, B. Bioconjugate Chem. 2000, 11, 414 (e) Wei, L.;
Banerjee, S.R.; Levadala, M.K.; Babich, J.; Zubieta, J. Inorg. Chim. Acta 2004, 357,
1499 (f) Jaouen, G.; Top, S.; Vessières, A.; Pigeon, P.; Leclercq, G.; Laios, I. Chem
Commun. 2001, 383 (g) Zhang, J.; Vittal, J.J.; Henderson, W.; Wheaton, J.R.; Hall, I.H.;
Hor, T.S.A.; Yan, Y.K. J. Organomet. Chem. 2002, 650, 123 (h) Heldt, J.-M.; FischerDurand, N.; Salmain, M.; Vessières, A.; Jaouen, G. J. Organomet. Chem. 2004, 689,
4775
74.
Yam, V.W.-W.; Li, B.; Yang, Y.; Chu, B.W.-K.; Wong, K.M.-C.; Cheung, K.-K. Eur. J.
Inorg. Chem. 2003, 4035 (b) Lundin, N.; Blackman, A.; Gordon, K.; Officer, D. Angew.
Chem. Int. Ed. 2006, 45, 2582 (c) Ranjan, S.; Lin, S.-Y.; Hwang, K.-C.; Chi, Y.; Ching,
W.-L.; Liu, C.-S. Inorg. Chem. 2003, 42, 1248 (d) Lee, P.-I.; Hsu, S.L.-C.; Chung, C.-T.
Synthetic Metals 2006, 156, 907 (e) Ng, P.K.; Gong, X.; Chan, S.H.; Lam, L.S.M.; Chan,
W.K. Chem. Eur. J. 2001, 7, 4358 (f) Wang, K.; Huang, L.; Gao, L.; Jin, L.; Huang, C.
Inorg. Chem. 2002, 41, 3353 (g) Lam, L.S.M.; Chan, W.K. Chem Phys Chem 2001, 4,
252
133
LIST OF REFERENCES (continued)
75.
Yam, V.W.-W.; Ko, C.-C.; Wu, L.-X.; Wong, K.M.-C.; Cheung, K.-K. Organometallics
2000, 19, 1820 (b) Sun, S.-S.; Lees, A.; Zavalij, P.Y. Inorg. Chem. 2003, 42, 3445 (c)
Sun, S.-S.; Tran, D.; Odongo, O.; Lees, A. Inorg. Chem. 2002, 41, 132 (d) Lewis, J.D.;
Perutz, R.N.; Moore, J.N. J. Phys. Chem. A 2004, 108, 9037 (e) Amendola, V.;
Bacchilega, D.; Costa, I.; Gianelli, L.; Montalti, M.; Pallavicini, P.; Perotti, A.; Prodi, L.;
Zaccheroni, N. J. Photochem. Photobio. A: Chem. 2003, 159, 249 (f) Lam, M.H.W.; Lee,
D.Y.K.; Man, K.W.; Lau, C.S.W. J. Mater. Chem. 2000, 10, 1825 (g) Cattaneo, M.;
Fagalde, F.; Katz, N.E. Inorg. Chem. 2006, 45, 6884 (h) Beer, P.D.; Timoshenko, V.;
Maestri, M.; Passaniti, P.; Balzani, V. Chem. Commun. 1999, 1755 (i) Curiel, D.; Beer,
P.D. Chem. Commun. 2005, 1909 (j) Pope, S.J.A.; Coe, B.J.; Faulkner, S. Chem.
Commun. 2004, 1550
76.
Kober, E. M.; Sullivan, B. P.; Dressick, W. J.; Caspar, J. V.; Meyer, T. J. J. Am. Chem.
Soc. 1980, 102, 1383
77.
Villegas, J. M.; Stoyanov, S. R.; Huang, W.; Rillema, D. P. Inorg. Chem. 2005, 44, 2297
78.
Kaim, W.; Kramer, H. E. A.; Vogler, C.; Rieker, J. J. Organometallic Chem. 1989, 367,
107
79.
MacQueen, D. B.; Eyler, J. R.; Schanze, K. S. J. Am. Chem. Soc. 1992, 114, 1897
80.
Klein, A.; Vogler, C. Kaim, W. Organometallics 1996, 15, 236
81.
Turro, N. J. Modern Molecular Photochemistry 1978, Benjamin, Menlo Park, California
82.
Balzani, V.; Moggi, L.; Manfrin, M. F.; Bolletta, F.; Laurence, G. S. Coord. Chem. Rev.
1975, 15, 321
83.
Balzani, V.; Bolletta, F.; Gandolfi, M. T.; Maestri, M. Top. Curr. Chem. 1978, 75, 1
84.
Kavarnos, G. J.; Turro, N. J. Chem. Rev. 1986, 86, 401
85.
Scandola, F.; Balzani, V. J. Chem. Educ. 1983, 60, 814
86.
Sutin, N.; Creutz, C. J. Chem. Educ. 1983, 60, 809
87.
Sutin, N.; Creutz, C. Adv. Chem. Ser. 1978, 168, 1
88.
Sutin, N.; Creutz, C. Pure Appl. Chem. 1980, 52, 2717
89.
Kalyanasundaram, K. Coord. Chem. Rev. 1982, 46, 159
134
LIST OF REFERENCES (continued)
90.
Seddon, E. A.; Seddon, K. R. The Chemistry of Ruthenium 1984, Elsevier, Amsterdam,
Chap. 15
91.
Sutin, N. Acc. Chem. Res. 1982, 15, 275
92.
Balzani, V.; Scandola, F. in M. Graetzel (Ed.) Energy Resources through Photochemistry
and Catalysis 1983, Academic Press, New York, 1
93.
Sutin, N. Prog. Inorg. Chem. 1983, 30, 441
94.
Marcus, R. A.; Sutin, N. Biochim. Biophys. Acta 1985, 811, 265
95.
Balzani, V.; Bolletta, F.; Scandola, F. J. Am. Chem. Soc. 1980, 102, 2152
96.
Wei, M.-Y.; Guo, L.-H.; Chen, H. Microchimica Acta 2006, 155(3-4), 409
97.
Xie, H.; Tansil, N. C.; Gao, Z. Frontiers in Bioscience 2006, 11(1), 1147
98.
Tan, Li-F.; Chao, H. Inorganica Chimica Acta 2007, 360(6), 2016
99.
Tan, Li-F.; Wang, F.; Chao, H.; Zhou, Y.-F.; Weng, C. Journal of Inorganic
Biochemistry 2007, 101(4), 700
100.
Tan, Li-F.; Wang, F.; Chao, H. Helvetica Chimica Acta 2007, 90(1), 205
101.
Gao, F.; Chao, H.; Zhou, F.; Xu, L.-C.; Zheng, K.-C.; Ji, L.-N. Helvetica Chimica Acta
2007, 90(1), 36
102.
Nagababu, P.; Latha, J. N. L.; Satyanarayana, S. Chemistry & Biodiversity 2006, 3(11),
1219
103.
Tan, Li-F.; Liu, X.-H.; Chao, H.; Ji, L.-N. Journal of Inorganic Biochemistry 2007,
101(1), 56
104.
Zhang, Y.; Bao, C.; Wang, G.; Song, Y.; Jiang, L.; Song, Y.; Wang, K.; Zhu, D. Surface
and Interface Analysis 2006, 38(10), 1372
105.
Uma Maheswari, P.; Rajendiran, V.; Palaniandavar, M.; Thomas, R.; Kulkarni, G. U.
Inorganica Chimica Acta 2006, 359(14), 4601
106.
Liu, Y.-J.; Chao, H.; Yuan, Yi-X.; Yu, H.-J.; Ji, L.-N. Inorganica Chimica Acta 2006,
359(12), 3807
135
LIST OF REFERENCES (continued)
107.
Smith, J. A.; Morgan, J. L.; Turley, A. G.; Collins, J. G.; Keene, F. R. Dalton
Transactions 2006, 26, 3179
108.
Spillane, C. B.; Morgan, J. L.; Fletcher, N. C.; Collins, J. G.; Keene, F. R. Dalton
Transactions 2006, 25, 3122
109.
Lawrence, D.; Vaidyanathan, V. G.; Nair, B. U. Journal of Inorganic Biochemistry 2006,
100(7), 1244
110.
Morgan, J. L.; Buck, D. P.; Turley, A. G.; Collins, J. G.; Keene, F. R. Inorganica
Chimica Acta 2006, 359(3), 888
111.
Wu, J.-Z.; Yuan, L.; Yu, Y. Inorganica Chimica Acta 2006, 359(2), 718
112.
Fukuzumi, S.; Tanaka, M.; Nishimine, M.; Ohkubo, K. Journal of Photochemistry and
Photobiology, A: Chemistry 2005, 175(2-3), 79
113.
Chouai, A.; Wicke, S. E.; Turro, C.; Bacsa, J.; Dunbar, K. R.; Wang, D.; Thummel, R. P.
Inorganic Chemistry 2005, 44(17), 5996
114.
Deng, H.; Li, J.; Zheng, K. C.; Yang, Y.; Chao, H.; Ji, L. N. Inorganica Chimica Acta
2005, 358(12), 3430
115.
Nordell, P.; Lincoln, P. Journal of the American Chemical Society 2005, 127(27), 9670
116.
Shi, S.; Liu, J.; Li, J.; Zheng, K. C.; Tan, C. P.; Chen, L. M.; Ji, L. N. Dalton
Transactions 2005, 11, 2038
117.
Liu, Y.-J.; Chao, H.; Tan, L.-F.; Yuan, Y.-X.; Wei, W.; Ji, L.-N. Journal of Inorganic
Biochemistry 2005, 99(2), 530
118.
Jiang, C.-W. European Journal of Inorganic Chemistry 2004, 11, 2277
119.
Liu, F.; Wang, K.; Bai, G.; Zhang, Y.; Gao, L. Inorganic Chemistry 2004, 43(5), 1799
120.
Wu, J.-Z.; Yuan, L. Journal of Inorganic Biochemistry 2004, 98(1), 41
121.
Copeland, K. D.; Lueras, A. M. K.; Stemp, E. D. A.; Barton, J. K. Biochemistry 2002,
41(42), 12785
122.
Liu, J.-G.; Ji, L.-N. Journal of the Indian Chemical Society 2000, 77(11-12), 539
136
LIST OF REFERENCES (continued)
123.
Zou, X.-H.; Ye, B.-H.; Li, H.; Zhang, Q.-L.; Chao, H.; Liu, J.-G.; Ji, L.-N.; Li, X.-Y.
JBIC, Journal of Biological Inorganic Chemistry 2001, 6(2), 143
124.
Liu, J.-G.; Ye, B.-H.; Li, H.; Zhen, Q.-X.; Ji, L.-N.; Fu, Y.-H. Journal of Inorganic
Biochemistry 1999, 76(3-4), 265
125.
Neumann, H. M.; Van Meter, F. M. J. Am. Chem. Soc. 1976, 98, 1382
126.
Ortega, F.; Rodenas, E. J. Phys. Chem. 1986, 90, 2408
127.
Lee, T. S.; Kolthoff, I. M.; Leussing, D. L. J. Am. Chem. Soc. 1948, 70, 3596
128.
Blandamer, M. J.; Burgess, J.; Fawcett, J.; Guardado, P.; Hubbard, C. D.; Nuttall, S.;
Prouse, L. J. S.; Radulović, Russell, D. R. Inorg. Chem. 1992, 31, 1383
129.
Lawrance, G. A.; Stranks, D. R.; Suvachittanont, S. Inorg. Chem. 1979, 18, 82
130.
131.
Blandamer, M. J.; Burgess, J. Pure & Appl. Chem. 1982, 54, 2285
Dickens, J. E.; Basolo, F.; Neumann, H. M. J. Am. Chem. Soc. 1957, 79, 1286
132.
Ortega, F.; Rodenas, E. Can. J. Chem. 1989, 67, 305
133.
Blanamer, M. J.; Burgess, J.; Clark, B. J. Chem. Soc., Chem. Commun. 1983, 660
134.
Burgess, J.; Prince, R. H. J. Chem. Soc. 1965, 4697
135.
Margerum, D. W.; Morgenthaler, L. P. J. Am. Chem. Soc. 1962, 84, 706
136.
Blandamer, M. J.; Burgess, J. Pure & Appl. Chem. 1983, 55, 55
137.
Toma, L. M.; Eller, C.; Rillema, D. P.; Ruiz-Pérez, C.; Julve, M. Inor. Chim. Acta 2004,
357, 2609
138.
Gillard, R. D.; Knight, D. W.; Williams, P. A. Transition Met. Chem 1979, 4, 375
139.
Braterman, P. S.; Song, J.-I.; Peacock, R. D. Inorg. Chem. 1992, 31, 555
140.
Ruminski, R. R.; Van Tassel, K. D.; Peterson, J. D. Inorg. Chem. 1984, 23, 4380
141.
Constable, E. C.; Ward, M. D.; Corr, S. Inor. Chim. Acta 1988, 141, 201
142.
Krumholz, P. Inorg. Chem. 1965, 4, 612
137
LIST OF REFERENCES (continued)
143.
Palmer, R. A.; Piper, T. S. Inorg.Chem. 1966, 5, 864
144.
Burgess, J.; Prince, R. H. J. Chem. Soc. 1965, 6061
145.
Basolo, F.; Hayes, J. C.; Neumann, H. M. J. Am. Chem. Soc. 1954, 76, 3807
146.
Song, J.-I. Ph.D. Thesis, University of Glasgow, Scotland, 1989
147.
Stoyanov, S. R.; Villegas, J. M.; Rillema, D. P. Inorg. Chem. Commun. 2004, 7, 838
148.
Villegas, J. M.; Stoyanov, S. R.; Huang, W.; Lockyear, L. L.; Reibenspies, J. H.; Rillema,
D. P. Inorg. Chem. 2004, 43, 6383
149.
Fantacci, S.; De Angelis, F.; Sgamellotti, A.; Re, N. Chemical Physics Letters 2004, 396,
43
150.
Vlcek, A., Jr; Zalis, S. J. Phys. Chem. A 2005, 109, 2991
151.
Lafferty, J. J.; Case, F. H. J. Org. Chem. 1967, 32, 1591
152.
Eller, C.; Smucker, B.; Eichhorn, D.M.; Rillema, D.P.; Kirgan, R. Acta Cryst. 2004, E60,
o433-o434
153.
Gaussian 03, Revision B.04, Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G.
E.; Robb, M. A. ; Cheeseman, J. R.; Montgomery, Jr., J. A.; Vreven, T.; Kudin, K. N.;
Burant, J. C.; Millam, J. M.; Iyengar, S. S.; Tomasi, J.; Barone, V.; Mennucci, B.; Cossi,
M.; Scalmani, G.; Rega, N.; Petersson, G. A.; Nakatsuji, H.; Hada, M.; Ehara, M.;
Toyota, K.; Fukuda, R.; Hasegawa, J.; Ishida, M.; Nakajima, T.; Honda, Y.; Kitao, O.;
Nakai, H.; Klene, M.; Li, X.; Knox, J. E.; Hratchian, H. P.; Cross, J. B.; Bakken, V.;
Adamo, C.; Jaramillo, J.; Gomperts, R.; Stratmann, R. E.; Yazyev, O.; Austin, A. J.;
Cammi, R.; Pomelli, C.; Ochterski, J. W.; Ayala, P. Y.; Morokuma, K.; Voth, G. A.;
Salvador, P.; Dannenberg, J. J.; Zakrzewski, V. G.; Dapprich, S.; Daniels, A. D.; Strain,
M. C.; Farkas, O.; Malick, D. K.; Rabuck, A. D.; Raghavachari, K.; Foresman, J. B.;
Ortiz, J. V.; Cui, Q.; Baboul, A. G.; Clifford, S.; Cioslowski, J.; Stefanov, B. B.; Liu, G.;
Liashenko, A.; Piskorz, P.; Komaromi, I.; Martin, R. L.; Fox, D. J.; Keith, T.; Al-Laham,
M. A.; Peng, C. Y.; Nanayakkara, A.; Challacombe, M.; Gill, P. M. W.; Johnson, B.;
Chen, W.; Wong, M. W.; Gonzalez, C.; and Pople, J. A.; Gaussian, Inc., Wallingford CT,
2004
154.
(a) Becke, A. D. J. Chem. Phys. 1993, 98, 5648. (b) Lee, C.; Yang, W.; Parr, R. G. Phys.
Rev. B 1988, 37, 785. (c) Vosko, S. H.; Wilk, L.; Nusair, M. Can. J. Phys. 1980, 58,
1200. (d) Andrae, D.; Hauessermann, U.; Dolg, M.; Stoll, H.; Preuss, H. Theor.
Chim.Acta 1990, 77, 123
138
LIST OF REFERENCES (continued)
155.
(a) Stratmann, R. E.; Scuseria, G. E.; Frisch, M. J. J. Chem. Phys. 1998, 109, 8218. (b)
Bauernschmitt, R.; Ahlrichs, R. Chem. Phys. Lett. 1996, 256, 454. (c) Casida, M. E.;
Jamorski, C.; Casida, K. C.; Salahub, D. R. J. Chem. Phys. 1998, 108, 4439
156.
(a) Cossi, M.; Barone, V. J. Chem. Phys. 2001, 115, 4708. (b) Barone, V.; Cossi, M. J.
Phys. Chem. A 1998, 102, 1995. (c) Cossi, M.; Rega, N.; Scalmani, G.; Barone, V. J.
Comput. Chem. 2003, 24, 669
157.
The CPCM is designed to account for the bulk physical properties of the solvent. It does
not account for specific solvent-solute interactions. The TDDFT is known to perform
well for the computing of charge-transfer excited states between closely spaced moieties.
The tandem use of CPCM and TDDFT is currently the most suitable computational
approach for the treatment of the solvent effects to the transition metal complexes
excited-state energies.
158.
Frisch, Æ.; Frisch, M. J.; Trucks, G. W. Gaussian 03 User’s Reference, version 7.0;
Gaussian, Inc.: Carnegie, PA, 2003; p 206.
159.
(a) Stoyanov, S. R.; Villegas, J. M.; Cruz, A. J.; Lockyear, L. L.; Reibenspeis, J. H.;
Rillema, D. P. J. Chem. Theory Comput. 2005, 1, 95 (b) Lin, R.; Fu, Y.; Brock, C. P.;
Guarr, T. F. Inorg. Chem. 1992, 31, 4346
Bruker APEX2 User Manual 2006, Bruker AXS Inc., Madison, Wisconsin, USA. (b)
Sheldrick, G. M. SHELXS97 and SHELXL97 1997, University of Gőttingen, Germany.
160.
161.
Farrugia, L. J. J. Appl. Cryst 1999, 32, 837-838.
162.
Shaver, R. J.; Perkovic, M. W.; Rillema, D. P.; Woods, C. Inorg. Chem. 1995, 34, 5446
163.
Garber, T.; Van Wallendael, S.; Rillema, D. P.; Kirk, M.; Hatfield, W. E.; Welch, J. H.;
Singh, P. Inorg. Chem. 1990, 29, 2863
164.
Rillema, D. P.; Allen, G.; Meyer, T. J.; Conrad, D. Inorg. Chem. 1983, 22, 1617
165.
Calvert, J. G.; Pitts Jr., J. N. Photochemistry, John Wiley & Sons, United States of
America, 1966
166.
Demas, J. N.; Crosby, G. A. J. Amer. Chem. Soc. 1971, 93, 2841
167.
Kirgan, R. A.; Rillema, D. P. J. Photochem. Photobiol. submitted for publication.
168.
Ross, H. B.; Boldaji, M.; Rillema, D. P.; Blanton, C. B.; White, R. P. Inorg. Chem. 1989,
28, 1013
139
LIST OF REFERENCES (continued)
169.
Kirgan, R.; Simpson, M.; Moore, C.; Day, J.; Bui, L.; Tanner, C.; Rillema, D. P. Inorg.
Chem 2007, 46, 6464
170.
Barone, V.; Fabrizi de Biani, F.; Riuz, E.; Sieklucka, B. J. Am. Chem. Soc. 2001, 123,
10742
171.
Monat, J. E.; Rodriguez, J. H.; McCusker, J. K. J. Phys. Chem. A 2002, 106, 7399
172.
Rodriguez, J. H.; Wheeler, D. E.; McCusker, J. K. J. Am. Chem. Soc. 1998, 120, 12051
173.
Hughes, H. P.; Martin, D.; Bell, S.; McGarvey, J. J.; Vos, J. G. Inorg. Chem. 1993, 32,
4402
174.
Crutchley, R. J.; Lever, B. P. Inorg. Chem. 1982, 21, 2276
175.
Jordan, R. B. Reaction Mechanisms of Inorganic and Organometallic Systems 1991, New
York, Oxford University Press
176.
O’Boyle, N. M.; Vos, J. G. Gaussum 1.0 2005, Dublin City University
177.
Heilmann, J.; Lerner, H.-W.; Bolte, M. Acta Cryst., Sect. E: Struct. Rep. Online 2006, 62,
m1477
178.
Baker, J.; Engelhardt, L. M.; Figgis, B. N.; White, A. H. J. Chem. Soc., Dalton Trans.
1975, 530
179.
Baker, A. T.; Goodwin, H. A. Aust. J. Chem. 1985, 38, 207
180.
Gütlich, P. Struct. Bonding 1981 Berlin, 44 (references therein).
181.
Stoyanov, S. R.; Villegas, J. M.; Rillema, D. P. Inorg. Chem. 2003, 42, 7852
182.
Salignac, B. Inor. Chem. 2003, 42, 3516-3526.
183.
Deshpande, M. S., Kumbhar, A. S., Puranik, V. G. & Selvaraj, K. Crystal Growth &
Design 2006, 6(3), 743-748.
184.
Elemans, J., de Gelder, R., Rowan, A. & Nolte, R. Chem. Commun. 1998, 15, 1553-1554
185.
Elemans, J., Rowan, A. & Nolte, R. J. Am. Chem. Soc. 2002, 124(7), 1532-1540.
186.
Kurth, D., Fromm, K. & Lehn, J.-M. Eur. J. Inor. Chem. 2001, 6, 1532-1526.
140
LIST OF REFERENCES (continued)
187.
Hamiliton, W. C. & Ibers, J. A. Hydrogen Bonding in Solids 1968, W. A. Benjamin, New
York, p. 16
188.
Demas, J. N.; Crosby, G. A. J. Phys. Chem. 1971, 75, 991
189.
Casper, J. V.; Meyer, T. J. J. Am. Chem. Soc. 1983, 105, 5583
190.
Klassen, D. M.; Crosby, G. A. J. Chem. Phys. 1968, 48, 1853
191.
Demas, J. N.; Turner, T. F.; Crosby G. A. Inorg. Chem. 1969, 8, 674
192.
Origin 6.1, version 6.1052(B232), 2000, OriginLab Corporation: Northampton, MA
193.
Shaver, R.; Van Wallendael, S.; Rillema, D. P. J. Chem. Ed. 1991, 68, 604
194.
Snare, M. J.; Treloar, F. E.; Ghiggino, K. P.; Thistlethwaite, P. J. J. Photochem. 1982, 18,
335
195.
Magde, D.; Rojas, G.E.; Seybold, P. Photochem. Photobiol. 1999, 70, 737
141
APPENDICES
142
APPENDIX A
CHAPTER 2 SUPPLEMENTARY INFORMATION
Bipyrazine Complexes
Cartesian Coordinates from calculations
Chloride
Atom
Re
C
O
C
O
C
O
Cl
C
C
C
C
H
C
H
C
C
C
H
H
N
N
H
H
N
N
Coordinates
x
0.882643
2.227077
3.008462
2.226498
3.007042
1.176160
1.347703
0.370429
-3.241611
-1.959397
-2.079844
-0.786095
-1.915153
-2.079979
0.190882
-3.241853
-0.786707
-1.960136
0.190094
-1.916111
-0.840631
-0.840937
-4.230875
-4.230945
-3.191352
-3.191897
y
0.000019
1.376534
2.248334
-1.377889
-2.251048
0.003036
0.005518
-0.003399
1.534680
3.455529
0.734128
2.687442
4.538919
-0.733554
3.150780
-1.533875
-2.687057
-3.454948
-3.150671
-4.538351
1.328468
-1.328098
1.093332
-1.092349
2.885127
-2.884340
143
z
0.061549
-0.201819
-0.381743
-0.197546
-0.374411
1.966080
3.144606
-2.436084
0.052520
0.104072
0.095516
0.148543
0.101406
0.096027
0.177044
0.051786
0.151829
0.106651
0.181789
0.105070
0.147003
0.149233
0.008878
0.006097
0.056477
0.056919
APPENDIX A (continued)
Pyridine Derivative
Atom
Re
C
O
C
O
C
O
C
C
C
C
H
C
H
C
C
C
H
H
N
N
N
C
C
C
H
C
H
C
H
H
H
H
H
N
N
Coordinates
x
y
-0.489552 -0.822571
-1.732642 -1.366665
-2.462598 -1.669340
-1.744696 -1.412683
-2.482461 -1.744356
0.322373 -2.596562
0.826548 -3.663222
3.140808 1.205697
2.096061 0.508468
2.116770 0.630108
1.057060 -0.067134
2.100886 0.452536
2.109910 0.604972
0.237809 -0.586349
3.126466 1.152804
1.030883 -0.158337
2.062792 0.390459
0.206682 -0.692471
2.056955 0.297605
1.057700 -0.000759
1.044968 -0.045952
-1.368404 1.248853
-1.682229 1.864095
-1.649947 1.915388
-2.270405 3.133508
-1.469253 1.316258
-2.237041 3.186467
-1.412004 1.407858
-2.555769 3.813205
-2.505984 3.568918
-2.446211 3.664074
-3.018097 4.795361
3.984916 1.715341
3.975235 1.676882
3.133029 1.153464
3.105740 1.054315
144
z
-0.016506
-1.408209
-2.287906
1.345000
2.207642
-0.043632
-0.059983
-1.498542
-3.441581
-0.714940
-2.690934
-4.524705
0.755403
-3.171575
1.568088
2.696220
3.476102
3.151288
4.556687
-1.329714
1.338094
0.014719
1.195324
-1.145869
1.253307
2.104929
-1.164191
-2.072426
0.054707
2.218513
-2.115437
0.069847
-1.047322
1.142913
-2.849641
2.916499
Detailed Orbital Distributions
Chloride Derivative
71
H-7
-8.54
72
H-6
-8.49
73
H-5
-8.25
74
H-4
-7.74
75
H-3
-7.69
76
H-2
-7.17
77
H-1
-6.57
78
HOMO
-6.48
%Re
%CO
%Cl
%Bpz
0.530
0.142
0.308
99.02
1.740
0.342
0.509
97.41
0.546
0.364
0.413
98.68
12.79
11.95
73.30
1.954
33.85
11.05
46.65
8.449
32.39
11.62
49.93
6.064
68.36
29.17
0.264
2.209
34.93
14.86
45.64
4.574
39.48
18.08
41.31
1.133
%Total
100
100
100
100
100
100
100
100
100
Type
Bpz
Bpz
Bpz
Re, CO, Cl
Re, CO, Cl
Re, CO, Cl
Re, CO
Re, CO, Cl
Re, CO, Cl
Orbital
Energy
79
LUMO
-3.95
80
L+1
-3.01
81
L+2
-2.96
82
L+3
-1.6
83
L+4
-1.42
84
L+5
-1.4
85
L+6
-0.78
86
L+7
-0.4
87
L+8
-0.3
%Re
%CO
%Cl
%Bpz
3.168
4.688
1.857
90.29
0.466
2.244
0.007
97.28
0.474
0.922
0.321
98.28
20.24
74.50
1.013
4.247
20.96
73.79
4.071
1.176
2.140
2.736
0.006
95.12
0.435
98.03
0.195
1.343
89.24
7.799
0.200
2.760
43.49
52.31
0.841
3.357
%Total
100
100
100
100
100
100
100
100
100
Type
Bpz
Bpz
Bpz
Re, CO
Re, CO
Bpz
CO
Re
Re, CO
145
APPENDIX A (continued)
145
Orbital
Energy
70
H-8
-8.61
Pyridine Derivative
83
H-7
-12.25
84
H-6
-11.5
85
H-5
-11.49
86
H-4
-11.24
87
H-3
-11.19
88
H-2
-10.3
89
H-1
-10.12
90
HOMO
-10.11
%Re
%CO
%Bpz
%Py
2.478
8.938
11.31
77.28
2.624
1.420
3.093
92.86
0.156
0.029
73.23
26.58
0.472
0.289
26.45
72.79
1.785
0.555
97.53
0.126
0.306
0.299
99.36
0.036
69.03
28.11
2.549
0.310
67.80
26.74
4.570
0.892
62.34
23.28
8.490
5.887
%Total
100
100
100
100
100
100
100
100
100
Type
Orbital
Energy
Py
91
LUMO
-6.93
Py
92
L+1
-5.93
Bpz, Py
93
L+2
-5.86
Bpz, Py
94
L+3
-5.38
Bpz
95
L+4
-4.8
Bpz
96
L+5
-4.63
Re, CO
97
L+6
-4.44
Re, CO
98
L+7
-4.31
Re, CO
99
L+8
-3.81
%Re
%CO
%Bpz
%Py
3.553
4.735
91.18
0.531
0.172
2.495
97.02
0.312
0.747
1.294
96.38
1.577
1.570
4.018
1.633
92.78
22.87
56.92
0.273
19.93
7.680
16.30
2.735
73.29
21.66
75.01
2.197
1.133
1.512
1.262
94.67
2.555
0.762
95.61
1.687
1.936
%Total
100
100
100
100
100
100
100
100
100
Type
Bpz
Bpz
Bpz
Py
Re, CO
Py
Re, CO
Bpz
CO
146
APPENDIX A (continued)
146
Orbital
Energy
82
H-8
-12.9
APPENDIX A (continued)
TDDFT Singlet State Results
Calculated Singlet Excited States in Acetonitrile
Chloride Derivative
Excited state symmetry could not be determined.
Excited State 1: Singlet-?Sym 2.3757 eV 521.89 nm f=0.0038
78 -> 79
0.70051
This state for optimization and/or second-order correction.
Total Energy, E(RPA) = -1405.94240077
Copying the excited state density for this state as the 1-particle RhoCI density.
Excited state symmetry could not be determined.
Excited State 2: Singlet-?Sym 2.6071 eV 475.56 nm f=0.0759
77 -> 79
0.68011
Excited state symmetry could not be determined.
Excited State 3: Singlet-?Sym 2.7951 eV 443.57 nm f=0.0002
76 -> 79
0.70229
Excited state symmetry could not be determined.
Excited State 4: Singlet-?Sym 3.4695 eV 357.35 nm f=0.0315
74 -> 79
0.15412
78 -> 80
0.68096
Excited state symmetry could not be determined.
Excited State 5: Singlet-?Sym 3.5353 eV 350.70 nm f=0.0057
73 -> 79
-0.17707
77 -> 80
0.67439
Excited state symmetry could not be determined.
Excited State 6: Singlet-?Sym 3.5855 eV 345.79 nm f=0.0001
72 -> 79
-0.29316
73 -> 79
-0.40896
75 -> 79
0.41663
77 -> 80
-0.12601
78 -> 81
0.14072
Excited state symmetry could not be determined.
Excited State 7: Singlet-?Sym 3.6090 eV 343.54 nm f=0.0001
73 -> 79
0.18074
78 -> 81
0.67715
147
APPENDIX A (continued)
Excited state symmetry could not be determined.
Excited State 8: Singlet-?Sym 3.6535 eV 339.36 nm f=0.0159
71 -> 79
-0.46505
74 -> 79
0.46698
77 -> 81
-0.11637
Excited state symmetry could not be determined.
Excited State 9: Singlet-?Sym 3.7130 eV 333.92 nm f=0.0050
71 -> 79
-0.15416
77 -> 81
0.68251
Excited state symmetry could not be determined.
Excited State 10: Singlet-?Sym 3.7814 eV 327.88 nm f=0.0079
72 -> 79
0.53602
75 -> 79
0.42242
Excited state symmetry could not be determined.
Excited State 11: Singlet-?Sym 3.8591 eV 321.28 nm f=0.0712
71 -> 79
0.46584
74 -> 79
0.48294
77 -> 81
0.10358
78 -> 80
-0.10143
Excited state symmetry could not be determined.
Excited State 12: Singlet-?Sym 3.8687 eV 320.48 nm f=0.0007
76 -> 80
0.69290
Excited state symmetry could not be determined.
Excited State 13: Singlet-?Sym 4.0333 eV 307.40 nm f=0.0049
76 -> 81
0.19302
77 -> 83
0.21003
78 -> 82
0.62397
Excited state symmetry could not be determined.
Excited State 14: Singlet-?Sym 4.0467 eV 306.38 nm f=0.0022
76 -> 82
0.14624
77 -> 82
0.59760
78 -> 83
-0.33164
Excited state symmetry could not be determined.
Excited State 15: Singlet-?Sym 4.0630 eV 305.15 nm f=0.0024
76 -> 81
0.66731
78 -> 82
-0.18966
148
APPENDIX A (continued)
Excited state symmetry could not be determined.
Excited State 16: Singlet-?Sym 4.0837 eV 303.61 nm f=0.0828
72 -> 79
-0.13392
73 -> 79
0.21873
75 -> 79
0.13761
76 -> 82
-0.21496
77 -> 82
0.28542
78 -> 83
0.50135
Excited state symmetry could not be determined.
Excited State 17: Singlet-?Sym 4.0906 eV 303.09 nm f=0.2751
72 -> 79
-0.23476
73 -> 79
0.39881
75 -> 79
0.28273
75 -> 81
-0.11226
77 -> 80
0.11045
77 -> 82
-0.20762
78 -> 83
-0.25637
Excited state symmetry could not be determined.
Excited State 18: Singlet-?Sym 4.3960 eV 282.04 nm f=0.0107
70 -> 79
-0.10162
76 -> 83
0.27824
77 -> 83
0.52866
78 -> 82
-0.11051
78 -> 84
-0.20076
78 -> 85
-0.21057
Excited state symmetry could not be determined.
Excited State 19: Singlet-?Sym 4.4312 eV 279.80 nm f=0.0043
71 -> 80
0.38240
72 -> 81
-0.34211
73 -> 81
-0.32538
74 -> 80
-0.25219
75 -> 81
0.16614
Excited state symmetry could not be determined.
Excited State 20: Singlet-?Sym 4.4380 eV 279.37 nm f=0.0036
71 -> 79
0.10276
71 -> 81
0.36381
72 -> 80
-0.31401
73 -> 80
-0.31396
74 -> 81
-0.22828
149
APPENDIX A (continued)
75 -> 80
76 -> 83
77 -> 83
0.19033
-0.12118
0.12096
Excited state symmetry could not be determined.
Excited State 21: Singlet-?Sym 4.4843 eV 276.49 nm f=0.0027
70 -> 79
0.15558
76 -> 83
0.60891
77 -> 83
-0.15292
78 -> 84
0.12398
78 -> 85
0.12647
Excited state symmetry could not be determined.
Excited State 22: Singlet-?Sym 4.5564 eV 272.11 nm f=0.0279
70 -> 79
0.66026
Excited state symmetry could not be determined.
Excited State 23: Singlet-?Sym 4.6474 eV 266.78 nm f=0.0243
76 -> 82
0.47843
76 -> 84
-0.11080
76 -> 85
-0.11193
77 -> 84
-0.29435
77 -> 85
-0.29997
78 -> 83
0.14276
Excited state symmetry could not be determined.
Excited State 24: Singlet-?Sym 4.8124 eV 257.64 nm f=0.0728
71 -> 81
-0.15970
72 -> 80
0.26789
73 -> 80
-0.11694
75 -> 80
0.59071
Excited state symmetry could not be determined.
Excited State 25: Singlet-?Sym 4.8342 eV 256.47 nm f=0.0123
71 -> 80
0.12317
73 -> 81
-0.13352
74 -> 80
0.58926
75 -> 81
0.26956
77 -> 84
0.12862
77 -> 85
0.11062
Excited state symmetry could not be determined.
Excited State 26: Singlet-?Sym 4.8906 eV 253.51 nm f=0.0277
150
APPENDIX A (continued)
73 -> 80
74 -> 81
75 -> 80
0.46524
-0.47234
0.10337
Excited state symmetry could not be determined.
Excited State 28: Singlet-?Sym 4.9679 eV 249.57 nm f=0.0996
71 -> 80
-0.37343
72 -> 81
0.11571
73 -> 81
-0.24425
74 -> 80
-0.18623
75 -> 81
0.37582
76 -> 84
-0.17396
76 -> 85
-0.18812
Excited state symmetry could not be determined.
Excited State 29: Singlet-?Sym 5.0223 eV 246.87 nm f=0.0021
71 -> 81
0.22887
72 -> 80
0.51371
73 -> 80
-0.15029
74 -> 81
-0.27734
75 -> 80
-0.13293
78 -> 84
-0.14261
Excited state symmetry could not be determined.
Excited State 30: Singlet-?Sym 5.0365 eV 246.17 nm f=0.0391
71 -> 80
0.37568
72 -> 81
0.43824
73 -> 81
0.21102
74 -> 80
-0.10409
75 -> 81
0.25566
Excited state symmetry could not be determined.
Excited State 31: Singlet-?Sym 5.0715 eV 244.47 nm f=0.0088
71 -> 81
0.46560
72 -> 80
0.13462
73 -> 80
0.21572
74 -> 81
0.29563
77 -> 86
0.12029
78 -> 84
0.25640
Excited state symmetry could not be determined.
Excited State 32: Singlet-?Sym 5.0742 eV 244.34 nm f=0.0244
69 -> 79
-0.12035
151
APPENDIX A (continued)
71 -> 81
73 -> 80
74 -> 81
75 -> 80
76 -> 86
76 -> 88
77 -> 83
77 -> 86
77 -> 88
78 -> 84
78 -> 85
-0.18579
-0.18473
-0.15727
-0.10695
0.12832
-0.12593
0.15842
0.21888
0.16906
0.41525
0.16069
Excited state symmetry could not be determined.
Excited State 33: Singlet-?Sym 5.0985 eV 243.18 nm f=0.0004
76 -> 84
-0.14125
76 -> 85
-0.13172
78 -> 86
0.65223
Excited state symmetry could not be determined.
Excited State 34: Singlet-?Sym 5.1678 eV 239.92 nm f=0.0300
69 -> 79
0.16059
75 -> 80
0.11152
77 -> 86
0.13136
78 -> 84
-0.31226
78 -> 85
0.53950
Excited state symmetry could not be determined.
Excited State 35: Singlet-?Sym 5.1753 eV 239.57 nm f=0.0303
72 -> 81
-0.32904
73 -> 81
0.35210
75 -> 81
0.17227
77 -> 84
-0.31128
77 -> 85
0.31670
Excited state symmetry could not be determined.
Excited State 36: Singlet-?Sym 5.2834 eV 234.67 nm f=0.1089
68 -> 79
-0.10557
72 -> 81
-0.17155
73 -> 81
0.30251
75 -> 81
0.20531
77 -> 84
0.39138
77 -> 85
-0.34910
152
APPENDIX A (continued)
Excited state symmetry could not be determined.
Excited State 37: Singlet-?Sym 5.3089 eV 233.54 nm f=0.0149
77 -> 86
0.51184
77 -> 87
0.23180
77 -> 88
-0.32447
Excited state symmetry could not be determined.
Excited State 38: Singlet-?Sym 5.3235 eV 232.90 nm f=0.0062
76 -> 84
0.13899
77 -> 89
-0.22400
78 -> 87
-0.31467
78 -> 88
0.51805
Excited state symmetry could not be determined.
Excited State 39: Singlet-?Sym 5.3710 eV 230.84 nm f=0.0635
75 -> 83
0.14804
76 -> 82
0.18719
76 -> 84
0.27370
76 -> 85
0.19246
76 -> 89
0.25109
77 -> 85
0.23522
77 -> 89
-0.20064
78 -> 83
0.10151
78 -> 87
0.10629
78 -> 88
-0.19615
78 -> 90
0.13286
Excited state symmetry could not be determined.
Excited State 40: Singlet-?Sym 5.4236 eV 228.60 nm f=0.0006
69 -> 79
0.59868
70 -> 81
-0.10636
74 -> 81
-0.10901
75 -> 84
0.11744
78 -> 84
0.11689
78 -> 85
-0.10757
Excited state symmetry could not be determined.
Excited State 41: Singlet-?Sym 5.5195 eV 224.63 nm f=0.0021
72 -> 82
-0.11664
73 -> 82
0.12883
75 -> 82
-0.24233
76 -> 86
0.31539
77 -> 86
-0.13455
153
APPENDIX A (continued)
77 -> 88
78 -> 89
78 -> 91
-0.16902
0.44680
-0.10735
Excited state symmetry could not be determined.
Excited State 42: Singlet-?Sym 5.5317 eV 224.13 nm f=0.0101
70 -> 80
0.69845
Excited state symmetry could not be determined.
Excited State 43: Singlet-?Sym 5.5657 eV 222.77 nm f=0.0014
71 -> 82
0.19822
74 -> 82
0.64980
Excited state symmetry could not be determined.
Excited State 44: Singlet-?Sym 5.5963 eV 221.55 nm f=0.0033
72 -> 82
0.21228
73 -> 82
-0.22685
75 -> 82
0.50448
76 -> 86
0.15971
77 -> 86
-0.11010
78 -> 89
0.25887
Excited state symmetry could not be determined.
Excited State 45: Singlet-?Sym 5.5968 eV 221.53 nm f=0.0001
76 -> 84
-0.48138
76 -> 85
0.49075
Excited state symmetry could not be determined.
Excited State 46: Singlet-?Sym 5.6515 eV 219.38 nm f=0.0059
72 -> 83
0.20884
73 -> 83
-0.24249
74 -> 82
0.11726
75 -> 83
0.46078
77 -> 89
0.36571
Excited state symmetry could not be determined.
Excited State 47: Singlet-?Sym 5.6652 eV 218.85 nm f=0.0120
71 -> 83
0.13709
74 -> 83
0.43732
76 -> 86
-0.29914
76 -> 88
-0.12758
76 -> 90
0.10491
77 -> 87
0.13252
154
APPENDIX A (continued)
77 -> 88
78 -> 89
78 -> 91
-0.28482
0.10939
-0.10112
Excited state symmetry could not be determined.
Excited State 48: Singlet-?Sym 5.7130 eV 217.02 nm f=0.0064
70 -> 81
0.68580
Excited state symmetry could not be determined.
Excited State 49: Singlet-?Sym 5.7341 eV 216.22 nm f=0.0037
71 -> 83
0.12027
74 -> 83
0.42609
76 -> 86
0.19845
76 -> 87
-0.18045
76 -> 88
0.35907
76 -> 90
-0.10301
77 -> 87
-0.12965
77 -> 88
0.12642
78 -> 91
0.15996
Excited state symmetry could not be determined.
Excited State 50: Singlet-?Sym 5.7973 eV 213.87 nm f=0.0085
75 -> 83
-0.24511
76 -> 89
0.46042
77 -> 89
0.33054
77 -> 91
-0.18901
78 -> 87
-0.17245
78 -> 88
0.10659
Pyridine Derivative
Excited State 1: Singlet-?Sym 2.6711 eV 464.16 nm f=0.0045
89 -> 91
0.69747
This state for optimization and/or second-order correction.
Total Energy, E(RPA) = -1193.81449454
Copying the excited state density for this state as the 1-particle RhoCI density.
Excited state symmetry could not be determined.
Excited State 2: Singlet-?Sym 2.7896 eV 444.46 nm f=0.0523
88 -> 91
0.43158
90 -> 91
0.53706
Excited state symmetry could not be determined.
155
APPENDIX A (continued)
Excited State 3: Singlet-?Sym 2.8582 eV 433.78 nm f=0.0549
88 -> 91
0.55418
90 -> 91
-0.41121
Excited state symmetry could not be determined.
Excited State 5: Singlet-?Sym 3.5697 eV 347.32 nm f=0.0033
84 -> 91
0.67418
85 -> 92
-0.12264
Excited state symmetry could not be determined.
Excited State 6: Singlet-?Sym 3.7123 eV 333.98 nm f=0.0001
85 -> 91
0.10035
86 -> 91
-0.25970
90 -> 92
0.64431
Excited state symmetry could not be determined.
Excited State 7: Singlet-?Sym 3.8013 eV 326.17 nm f=0.0574
89 -> 92
0.65789
90 -> 93
0.21851
Excited state symmetry could not be determined.
Excited State 9: Singlet-?Sym 3.8783 eV 319.69 nm f=0.0304
86 -> 91
0.27661
88 -> 92
0.14977
89 -> 93
0.60744
90 -> 92
0.13971
Excited state symmetry could not be determined.
Excited State 10: Singlet-?Sym 3.9158 eV 316.63 nm f=0.0001
88 -> 92
0.67941
89 -> 93
-0.16268
Excited state symmetry could not be determined.
Excited State 11: Singlet-?Sym 3.9306 eV 315.43 nm f=0.0452
89 -> 92
-0.20164
90 -> 93
0.65863
Excited state symmetry could not be determined.
Excited State 12: Singlet-?Sym 4.1067 eV 301.90 nm f=0.0031
85 -> 92
0.10026
88 -> 93
0.67889
Excited state symmetry could not be determined.
156
APPENDIX A (continued)
Excited State 13: Singlet-?Sym
90 -> 95
0.69251
4.1105 eV 301.63 nm f=0.0000
Excited state symmetry could not be determined.
Excited State 14: Singlet-?Sym 4.1279 eV 300.36 nm f=0.3575
86 -> 91
0.50392
88 -> 95
-0.12321
89 -> 93
-0.29833
89 -> 94
0.11766
90 -> 92
0.20402
Excited state symmetry could not be determined.
Excited State 15: Singlet-?Sym 4.1912 eV 295.82 nm f=0.0027
89 -> 95
0.61354
90 -> 94
-0.25584
90 -> 96
0.15172
Excited state symmetry could not be determined.
Excited State 16: Singlet-?Sym 4.2377 eV 292.58 nm f=0.0066
88 -> 95
0.18271
89 -> 94
0.59806
89 -> 96
-0.30247
Excited state symmetry could not be determined.
Excited State 17: Singlet-?Sym 4.3550 eV 284.69 nm f=0.0005
84 -> 92
0.46215
85 -> 93
0.48807
Excited state symmetry could not be determined.
Excited State 18: Singlet-?Sym 4.3650 eV 284.04 nm f=0.0002
84 -> 91
0.10018
84 -> 93
0.42794
85 -> 92
0.47087
88 -> 93
-0.13392
90 -> 94
0.14200
Excited state symmetry could not be determined.
Excited State 19: Singlet-?Sym 4.4096 eV 281.17 nm f=0.0982
84 -> 93
-0.10571
85 -> 92
-0.12346
88 -> 94
0.29418
88 -> 96
-0.13675
89 -> 95
0.17796
157
APPENDIX A (continued)
90 -> 94
0.54958
Excited state symmetry could not be determined.
Excited State 20: Singlet-?Sym 4.4243 eV 280.23 nm f=0.0313
88 -> 95
-0.40417
89 -> 94
0.33199
89 -> 96
0.44392
Excited state symmetry could not be determined.
Excited State 21: Singlet-?Sym 4.5303 eV 273.68 nm f=0.0652
88 -> 94
0.58280
88 -> 96
-0.18731
89 -> 95
-0.12455
90 -> 94
-0.26804
90 -> 96
-0.11374
Excited state symmetry could not be determined.
Excited State 22: Singlet-?Sym 4.6034 eV 269.33 nm f=0.0029
88 -> 94
0.20442
88 -> 96
0.49150
88 ->100
0.10094
89 -> 99
-0.12421
90 -> 96
0.39911
Excited state symmetry could not be determined.
Excited State 23: Singlet-?Sym 4.6432 eV 267.02 nm f=0.0154
83 -> 91
0.69033
86 -> 92
0.10403
Excited state symmetry could not be determined.
Excited State 24: Singlet-?Sym 4.7313 eV 262.05 nm f=0.0038
88 -> 94
-0.11584
88 -> 96
-0.40986
89 -> 97
0.17370
89 -> 98
0.12968
89 -> 99
-0.27463
90 -> 96
0.41480
Excited state symmetry could not be determined.
Excited State 25: Singlet-?Sym 4.7503 eV 261.00 nm f=0.0331
88 -> 95
0.35275
88 -> 99
-0.14422
89 -> 96
0.35536
158
APPENDIX A (continued)
90 -> 97
90 -> 98
90 -> 99
0.26844
0.12792
-0.28821
Excited state symmetry could not be determined.
Excited State 26: Singlet-?Sym 4.8596 eV 255.13 nm f=0.0018
87 -> 92
0.70485
Excited state symmetry could not be determined.
Excited State 27: Singlet-?Sym 4.9087 eV 252.58 nm f=0.0117
84 -> 92
0.32655
84 -> 93
0.31121
85 -> 92
-0.23211
85 -> 93
-0.31172
86 -> 92
-0.32346
Excited state symmetry could not be determined.
Excited State 28: Singlet-?Sym 4.9115 eV 252.44 nm f=0.0125
84 -> 92
0.37421
84 -> 93
-0.25834
85 -> 92
0.15797
85 -> 93
-0.34694
86 -> 92
0.32252
Excited state symmetry could not be determined.
Excited State 29: Singlet-?Sym 4.9273 eV 251.62 nm f=0.0341
84 -> 93
0.32909
85 -> 92
-0.36109
86 -> 92
0.43444
Excited state symmetry could not be determined.
Excited State 30: Singlet-?Sym 4.9880 eV 248.57 nm f=0.0053
87 -> 93
0.49439
87 -> 94
-0.12711
88 -> 95
-0.10550
88 -> 97
-0.20272
88 -> 99
0.21916
90 -> 97
0.32602
Excited state symmetry could not be determined.
Excited State 31: Singlet-?Sym 5.0109 eV 247.43 nm f=0.0017
87 -> 93
0.47458
88 -> 97
0.22870
159
APPENDIX A (continued)
88 -> 98
88 -> 99
90 -> 97
90 -> 98
90 -> 99
0.12382
-0.26921
-0.21953
-0.10988
0.20293
Excited state symmetry could not be determined.
Excited State 32: Singlet-?Sym 5.0947 eV 243.36 nm f=0.0061
87 -> 93
-0.15545
87 -> 94
-0.28354
88 -> 97
0.12840
88 -> 99
-0.14686
90 -> 97
0.39188
90 -> 98
-0.23379
90 -> 99
0.34411
Excited state symmetry could not be determined.
Excited State 33: Singlet-?Sym 5.1546 eV 240.53 nm f=0.0302
86 -> 93
0.11898
88 ->100
-0.11271
89 -> 97
0.63562
90 -> 96
-0.11049
Excited state symmetry could not be determined.
Excited State 34: Singlet-?Sym 5.1552 eV 240.50 nm f=0.1240
80 -> 91
0.13891
85 -> 93
-0.11081
86 -> 93
0.60893
89 -> 97
-0.12498
90 -> 98
0.13009
Excited state symmetry could not be determined.
Excited State 35: Singlet-?Sym 5.2515 eV 236.09 nm f=0.0369
81 -> 91
0.18402
82 -> 91
0.66510
Excited state symmetry could not be determined.
Excited State 36: Singlet-?Sym 5.2942 eV 234.19 nm f=0.0096
88 -> 97
0.37924
88 ->102
0.15021
89 ->100
0.47099
90 -> 98
0.10768
90 -> 99
-0.14992
160
APPENDIX A (continued)
90 ->102
-0.14361
Excited state symmetry could not be determined.
Excited State 37: Singlet-?Sym 5.3150 eV 233.27 nm f=0.0072
81 -> 91
0.55362
82 -> 91
-0.10185
89 -> 98
0.35168
Excited state symmetry could not be determined.
Excited State 38: Singlet-?Sym 5.3568 eV 231.45 nm f=0.0112
88 -> 97
-0.29542
88 -> 98
0.10717
88 -> 99
-0.16894
88 ->100
0.12746
88 ->102
-0.15585
89 -> 99
0.16828
89 ->100
0.34043
90 ->100
0.32589
Excited state symmetry could not be determined.
Excited State 39: Singlet-?Sym 5.3586 eV 231.37 nm f=0.0127
81 -> 91
0.10924
88 -> 97
0.21742
88 -> 99
0.12572
88 ->100
0.17550
88 ->102
0.11523
89 -> 98
-0.12858
89 -> 99
0.22802
89 ->100
-0.27446
90 ->100
0.41649
Excited state symmetry could not be determined.
Excited State 40: Singlet-?Sym 5.4409 eV 227.88 nm f=0.0123
86 -> 93
-0.12178
86 -> 94
0.12119
88 -> 97
-0.11900
88 -> 98
0.10273
88 -> 99
-0.10320
90 -> 98
0.56882
90 -> 99
0.29775
Excited state symmetry could not be determined.
Excited State 41: Singlet-?Sym 5.4538 eV 227.34 nm f=0.0302
161
APPENDIX A (continued)
88 ->101
88 ->103
89 -> 98
89 -> 99
90 -> 96
90 ->100
90 ->101
90 ->103
-0.26879
0.12496
0.15541
-0.23764
-0.11233
0.28985
0.39551
-0.17974
Excited state symmetry could not be determined.
Excited State 42: Singlet-?Sym 5.4797 eV 226.26 nm f=0.0609
83 -> 92
-0.10943
83 -> 97
0.14247
87 -> 94
0.30927
88 -> 98
-0.18387
88 -> 99
0.20934
88 ->102
-0.15005
89 ->100
0.12351
89 ->101
-0.15312
90 -> 97
0.11075
90 -> 99
0.14674
90 ->102
0.36969
Excited state symmetry could not be determined.
Excited State 43: Singlet-?Sym 5.5101 eV 225.01 nm f=0.0026
86 -> 94
0.68387
Excited state symmetry could not be determined.
Excited State 44: Singlet-?Sym 5.5344 eV 224.03 nm f=0.0001
87 -> 94
-0.12433
88 -> 97
0.21787
88 -> 98
-0.16095
88 -> 99
0.19366
88 ->102
-0.26596
89 ->101
0.40677
89 ->103
-0.18119
90 -> 99
0.19402
Excited state symmetry could not be determined.
Excited State 45: Singlet-?Sym 5.5401 eV 223.79 nm f=0.0166
81 -> 91
-0.26379
82 -> 91
0.10988
89 -> 98
0.50902
162
APPENDIX A (continued)
89 -> 99
0.32004
Excited state symmetry could not be determined.
Excited State 46: Singlet-?Sym 5.5860 eV 221.95 nm f=0.0124
83 -> 92
-0.11134
83 -> 97
0.17271
87 -> 94
0.37127
88 -> 97
-0.11153
88 -> 98
0.17058
88 -> 99
-0.12107
89 ->101
0.29955
89 ->103
-0.13501
90 -> 97
0.22405
90 -> 98
-0.13476
90 ->102
-0.17280
Excited state symmetry could not be determined.
Excited State 47: Singlet-?Sym 5.6167 eV 220.74 nm f=0.0042
85 -> 94
0.68711
Excited state symmetry could not be determined.
Excited State 48: Singlet-?Sym 5.6358 eV 219.99 nm f=0.0026
87 -> 95
0.69919
Excited state symmetry could not be determined.
Excited State 50: Singlet-?Sym 5.6693 eV 218.69 nm f=0.0005
84 -> 94
0.67305
88 ->100
-0.11883
89 ->102
0.11506
TDDFT Triplet State Results
Chloride Derivative
Excited state symmetry could not be determined.
Excited State 1: ?Spin -?Sym 0.0720 eV 17219.48 nm f=0.0000
74B -> 78B
0.92972
76B -> 78B
-0.15873
77B -> 78B
0.40864
Excited state symmetry could not be determined.
Excited State 2: ?Spin -?Sym 0.4702 eV 2636.92 nm f=0.0000
73B -> 78B
0.90267
163
APPENDIX A (continued)
74B -> 78B
76B -> 78B
77B -> 78B
-0.23452
-0.15197
0.40193
Excited state symmetry could not be determined.
Excited State 3: ?Spin -?Sym 0.6844 eV 1811.60 nm f=0.0009
79A -> 81A
-0.14095
79A -> 83A
-0.10917
75B -> 78B
0.92473
76B -> 78B
0.31417
77B -> 78B
0.11870
Excited state symmetry could not be determined.
Excited State 4: ?Spin -?Sym 0.7143 eV 1735.83 nm f=0.0012
79A -> 81A
0.10103
75B -> 78B
-0.32529
76B -> 78B
0.87245
77B -> 78B
0.34299
Excited state symmetry could not be determined.
Excited State 5: ?Spin -?Sym 0.7711 eV 1607.84 nm f=0.0000
73B -> 78B
-0.48761
74B -> 78B
-0.34634
76B -> 78B
-0.29387
77B -> 78B
0.74208
Excited state symmetry could not be determined.
Excited State 6: ?Spin -?Sym 1.1028 eV 1124.31 nm f=0.0108
79A -> 80A
0.93192
71B -> 78B
0.31969
Pyridine Derivative
Excited state symmetry could not be determined.
Excited State 1: ?Spin -?Sym -0.0184 eV -67338.59 nm f=-0.0000
91A -> 94A
-0.24668
80B -> 90B
0.11445
85B -> 90B
0.37220
86B -> 90B
1.53522
88B -> 90B
-0.80957
Excited state symmetry could not be determined.
Excited State 2: ?Spin -?Sym 0.1539 eV 8057.99 nm f=0.0001
164
APPENDIX A (continued)
85B -> 90B
86B -> 90B
88B -> 90B
89B -> 90B
-0.39365
0.52446
0.78195
-0.19672
Excited state symmetry could not be determined.
Excited State 3: ?Spin -?Sym 0.1575 eV 7873.08 nm f=0.0001
87B -> 90B
-0.11197
88B -> 90B
0.18100
89B -> 90B
0.98410
Excited state symmetry could not be determined.
Excited State 4: ?Spin -?Sym 0.3407 eV 3638.99 nm f=0.0000
85B -> 90B
0.96354
88B -> 90B
0.39551
Excited state symmetry could not be determined.
Excited State 5: ?Spin -?Sym 0.4085 eV 3034.79 nm f=0.0074
91A -> 95A
-0.30923
91A -> 96A
0.12529
87B -> 90B
0.91792
Excited state symmetry could not be determined.
Excited State 6: ?Spin -?Sym 1.1050 eV 1122.05 nm f=0.0046
91A -> 92A
0.96432
91A -> 93A
-0.11132
91A -> 94A
0.21359
165
APPENDIX A (continued)
Dimethyl-Bipyrazine Complexes
Cartesian Coordinates from calculations
Chloride Derivative
Atom
Re
C
O
C
O
C
O
Cl
C
C
C
C
C
H
C
C
C
H
N
N
H
H
N
N
C
H
H
H
C
H
H
H
Coordinates
x
-0.032140
-0.060797
-0.024576
-1.762530
-2.806341
-0.853463
-1.355889
1.140226
3.850900
4.121861
2.519678
2.791583
1.618045
2.368024
1.961618
-0.518621
-0.156288
-1.505915
1.994871
0.354144
4.295590
2.950797
4.642657
1.097257
5.015652
5.886399
5.394749
4.491439
-1.110690
-1.239075
-0.703191
-2.090184
y
0.073423
0.120900
0.148096
-0.804356
-1.363232
1.811442
2.889606
-2.190803
1.186809
1.693311
0.773998
1.289936
0.268447
1.322186
0.111326
-0.554605
-0.710351
-0.827588
0.837690
-0.070561
1.151293
0.367856
1.639412
-0.367840
2.185838
1.526635
3.186724
2.223603
-1.258570
-0.540898
-2.177864
-1.480806
166
z
-0.008687
1.930951
3.115339
-0.024087
-0.080793
-0.118011
-0.191863
0.039279
-1.747841
0.505723
-1.529658
0.741036
-2.568744
1.735668
-3.927890
-3.071972
-4.425674
-2.724786
-0.261794
-2.150702
-2.736362
-4.291132
-0.755228
-4.844458
1.611261
1.711877
1.373090
2.571132
-5.451367
-6.270440
-5.889115
-5.016925
APPENDIX A (continued)
Pyridine Derivative
Atom
Re
C
O
C
O
C
O
C
C
C
C
C
H
C
C
C
H
N
N
N
C
C
C
H
C
H
C
H
H
H
H
H
N
N
C
H
H
H
C
H
H
H
Coordinates
x
-0.005964
0.006173
0.065658
-1.859960
-2.983670
-0.580279
-0.919483
3.905562
4.301390
2.555092
2.957146
1.562011
2.573173
1.823057
-0.690620
-0.414199
-1.696745
2.092676
0.282979
0.703121
0.111967
1.711512
0.499721
-0.695452
2.151455
2.159173
1.538324
-0.011655
2.950059
1.854437
4.309195
2.820012
4.764657
0.861374
-1.482400
-1.569038
-1.210185
-2.458121
5.261707
6.147746
5.613930
4.806604
y
-0.034780
-0.063502
-0.081277
-0.614479
-0.981335
1.827410
2.958379
0.865996
1.210796
0.535514
0.868524
0.238471
0.882150
0.240055
-0.217553
-0.195670
-0.387516
0.527985
-0.010590
-2.169485
-3.080294
-2.608972
-4.425017
-2.720247
-3.938311
-1.879641
-4.869394
-5.104838
-4.232220
-5.907947
0.874552
0.421499
1.191967
0.023706
-0.401072
0.492988
-1.229194
-0.608556
1.607617
0.962304
2.632646
1.553268
167
z
0.017728
1.960159
3.141752
0.010193
-0.044350
0.040641
0.044883
-1.804852
0.465274
-1.557180
0.733311
-2.596036
1.745193
-3.983896
-3.082160
-4.467427
-2.720901
-0.261245
-2.153948
-0.058907
-0.890161
0.753502
-0.936365
-1.515512
0.760856
1.417089
-0.097559
-1.609456
1.433603
-0.107288
-2.811562
-4.370761
-0.819294
-4.902705
-5.503621
-6.133292
-6.168474
-5.054361
1.550398
1.526153
1.381262
2.543813
Detailed Orbital Distributions
Chloride Derivative
79
H-7
-8.25
80
H-6
-8.1
81
H-5
-8.09
82
H-4
-7.56
83
H-3
-7.52
84
H-2
-6.99
85
H-1
-6.39
86
HOMO
-6.31
%Re
%CO
%MeBpz
%Cl
1.814
0.379
97.16
0.649
0.971
0.310
98.07
0.651
1.078
0.398
97.69
0.833
12.62
11.89
2.310
73.18
33.70
11.12
8.423
46.76
31.43
11.39
7.561
49.62
68.19
29.41
2.147
0.259
35.29
15.27
3.921
45.52
39.71
18.28
1.097
40.91
% Total
100
100
100
100
100
100
100
100
100
Type
MeBpz
MeBpz
MeBpz
Cl
Re, Cl
Re, Cl
Re, CO
Re, CO, Cl
Re, CO, Cl
Orbital
Energy
87
LUMO
-3.66
88
L+1
-2.78
89
L+2
-2.68
90
L+3
-1.43
91
L+4
-1.26
92
L+5
-1.07
93
L+6
-0.62
94
L+7
-0.31
95
L+8
-0.13
%Re
%CO
%MeBpz
%Cl
2.891
4.745
90.55
1.819
0.388
2.227
97.38
0.005
0.485
0.596
98.71
0.214
20.42
76.91
1.657
1.004
20.66
74.03
1.287
4.022
1.703
1.073
97.22
0.002
0.452
97.51
1.840
0.201
100.00
0.000
0.000
0.000
37.71
57.62
3.799
0.868
% Total
100
100
100
100
100
100
100
100
100
Type
MeBpz
MeBpz
MeBpz
Re, CO
Re, CO
MeBpz
CO
Re, CO
Re, CO
168
APPENDIX A (continued)
168
Orbital
Energy
78
H-8
-8.31
Pyridine Derivative
91
H-7
-12.11
92
H-6
-11.36
93
H-5
-10.95
94
H-4
-10.9
95
H-3
-10.87
96
H-2
-10.1
97
H-1
-9.92
98
HOMO
-9.91
%Re
%CO
%MeBpz
%Py
0.056
0.078
99.22
0.649
2.339
1.379
3.778
92.50
0.283
0.236
0.204
99.28
1.855
0.642
97.40
0.099
0.558
0.220
99.20
0.022
0.819
0.236
98.87
0.077
68.82
28.26
2.626
0.294
67.18
26.86
5.129
0.835
62.60
23.69
8.016
5.688
%Total
100
100
100
100
100
100
100
100
100
Type
MeBpz
Py
Py
MeBpz
MeBpz
MeBpz
Re, CO
Re, CO
Re, CO
Orbital
Energy
99
LUMO
-6.58
100
L+1
-5.64
101
L+2
-5.52
102
L+3
-5.24
103
L+4
-4.62
104
L+5
-4.48
105
L+6
-4.26
106
L+7
-3.92
107
L+8
-3.63
%Re
%CO
%MeBpz
%Py
3.450
5.004
91.05
0.499
0.127
2.557
96.93
0.388
0.761
1.189
93.33
4.720
1.461
3.582
5.073
89.88
17.74
46.29
0.535
35.44
11.99
27.64
0.897
59.47
21.32
75.13
2.497
1.055
2.008
3.081
93.65
1.265
0.775
93.63
3.961
1.633
%Total
100
100
100
100
100
100
100
100
100
Type
MeBpz
MeBpz
MeBpz
Py
Re, CO
Re, CO,
Py
Re, Co
MeBpz
CO
169
APPENDIX A (continued)
169
Orbital
Energy
90
H-8
-12.32
APPENDIX A (continued)
TDDFT Singlet State Results
Chloride Derivative
Excited State 1: Singlet-?Sym 2.4802 eV 499.89 nm f=0.0030
86 -> 87
0.70038
This state for optimization and/or second-order correction.
Total Energy, E(RPA) = -1484.56970456
Copying the excited state density for this state as the 1-particle RhoCI density.
Excited state symmetry could not be determined.
Excited State 2: Singlet-?Sym 2.6980 eV 459.54 nm f=0.0722
85 -> 87
0.68170
Excited state symmetry could not be determined.
Excited State 3: Singlet-?Sym 2.9001 eV 427.52 nm f=0.0007
84 -> 87
0.70158
Excited state symmetry could not be determined.
Excited State 4: Singlet-?Sym 3.5217 eV 352.06 nm f=0.0341
81 -> 87
-0.13769
86 -> 88
0.68424
Excited state symmetry could not be determined.
Excited State 5: Singlet-?Sym 3.5710 eV 347.19 nm f=0.0007
82 -> 87
0.10163
83 -> 87
-0.22783
85 -> 88
0.65586
Excited state symmetry could not be determined.
Excited State 6: Singlet-?Sym 3.6221 eV 342.30 nm f=0.0028
80 -> 87
0.21035
82 -> 87
0.61287
83 -> 87
0.16631
Excited state symmetry could not be determined.
Excited State 7: Singlet-?Sym 3.6945 eV 335.59 nm f=0.0128
79 -> 87
0.40069
81 -> 87
0.52942
82 -> 88
0.11327
Excited state symmetry could not be determined.
Excited State 8: Singlet-?Sym 3.7023 eV 334.88 nm f=0.0237
170
APPENDIX A (continued)
83 -> 87
85 -> 88
86 -> 89
-0.23240
-0.11933
0.63913
Excited state symmetry could not be determined.
Excited State 9: Singlet-?Sym 3.8174 eV 324.79 nm f=0.0020
79 -> 87
0.11473
85 -> 89
0.69084
Excited state symmetry could not be determined.
Excited State 10: Singlet-?Sym 3.8289 eV 323.81 nm f=0.1480
80 -> 87
-0.43988
83 -> 87
0.41636
85 -> 88
0.15508
86 -> 89
0.24632
Excited state symmetry could not be determined.
Excited State 11: Singlet-?Sym 3.9210 eV 316.20 nm f=0.0100
82 -> 87
-0.10621
84 -> 88
0.68732
Excited state symmetry could not be determined.
Excited State 12: Singlet-?Sym 3.9514 eV 313.77 nm f=0.0684
79 -> 87
0.52930
81 -> 87
-0.41157
85 -> 89
-0.10926
Excited state symmetry could not be determined.
Excited State 13: Singlet-?Sym 3.9788 eV 311.61 nm f=0.2941
80 -> 87
0.47342
82 -> 87
-0.23699
83 -> 87
0.33502
84 -> 88
-0.10597
85 -> 88
0.12414
86 -> 89
0.14019
Excited state symmetry could not be determined.
Excited State 14: Singlet-?Sym 4.0287 eV 307.76 nm f=0.0063
85 -> 91
0.21938
86 -> 90
0.64752
Excited state symmetry could not be determined.
Excited State 15: Singlet-?Sym 4.0388 eV 306.99 nm f=0.0020
171
APPENDIX A (continued)
84 -> 90
85 -> 90
86 -> 91
0.14951
0.61106
-0.30408
Excited state symmetry could not be determined.
Excited State 16: Singlet-?Sym 4.0779 eV 304.04 nm f=0.0001
84 -> 90
-0.20105
85 -> 90
0.32003
86 -> 91
0.57698
Excited state symmetry could not be determined.
Excited State 17: Singlet-?Sym 4.1738 eV 297.05 nm f=0.0014
84 -> 89
0.68631
Excited state symmetry could not be determined.
Excited State 18: Singlet-?Sym 4.3927 eV 282.25 nm f=0.0128
84 -> 91
0.26986
85 -> 91
0.53260
86 -> 90
-0.11637
86 -> 92
-0.28925
Excited state symmetry could not be determined.
Excited State 19: Singlet-?Sym 4.4315 eV 279.78 nm f=0.0027
79 -> 88
-0.32548
80 -> 89
0.25789
81 -> 88
-0.33836
82 -> 89
0.41479
Excited state symmetry could not be determined.
Excited State 20: Singlet-?Sym 4.4388 eV 279.32 nm f=0.0030
79 -> 87
-0.11546
79 -> 89
-0.29109
80 -> 88
0.23875
81 -> 89
-0.28014
82 -> 88
0.42917
84 -> 89
0.11863
84 -> 91
-0.13987
85 -> 91
0.10736
Excited state symmetry could not be determined.
Excited State 21: Singlet-?Sym 4.4839 eV 276.51 nm f=0.0046
82 -> 88
0.11749
84 -> 89
0.10398
172
APPENDIX A (continued)
84 -> 91
85 -> 91
86 -> 92
0.61440
-0.15974
0.17753
Excited state symmetry could not be determined.
Excited State 22: Singlet-?Sym 4.6283 eV 267.88 nm f=0.0396
78 -> 87
0.53943
83 -> 88
0.38769
Excited state symmetry could not be determined.
Excited State 23: Singlet-?Sym 4.6427 eV 267.05 nm f=0.0283
84 -> 90
0.47798
84 -> 92
-0.15087
85 -> 92
-0.41159
85 -> 93
0.11225
86 -> 91
0.14095
Excited state symmetry could not be determined.
Excited State 24: Singlet-?Sym 4.7085 eV 263.32 nm f=0.0896
78 -> 87
-0.42341
83 -> 88
0.51158
Excited state symmetry could not be determined.
Excited State 25: Singlet-?Sym 4.8541 eV 255.42 nm f=0.0073
79 -> 88
-0.18873
81 -> 88
0.49475
82 -> 89
0.24562
83 -> 89
0.32718
85 -> 92
-0.14983
Excited state symmetry could not be determined.
Excited State 26: Singlet-?Sym 4.8854 eV 253.79 nm f=0.0058
79 -> 89
0.14670
80 -> 88
-0.36689
81 -> 89
0.29914
82 -> 88
0.48986
Excited state symmetry could not be determined.
Excited State 27: Singlet-?Sym 4.9122 eV 252.40 nm f=0.0135
83 -> 89
0.25740
84 -> 90
0.16986
84 -> 92
-0.37975
84 -> 93
0.10523
173
APPENDIX A (continued)
85 -> 92
86 -> 94
0.41371
-0.12127
Excited state symmetry could not be determined.
Excited State 28: Singlet-?Sym 4.9661 eV 249.66 nm f=0.2997
76 -> 87
0.11161
80 -> 89
-0.18560
81 -> 88
-0.32422
82 -> 89
-0.12655
83 -> 89
0.46648
84 -> 92
0.20893
Excited state symmetry could not be determined.
Excited State 29: Singlet-?Sym 4.9921 eV 248.36 nm f=0.0197
79 -> 88
0.53663
80 -> 88
-0.10325
82 -> 89
0.39337
84 -> 92
0.11303
Excited state symmetry could not be determined.
Excited State 30: Singlet-?Sym 5.0012 eV 247.91 nm f=0.0034
77 -> 87
0.14431
79 -> 88
0.11031
79 -> 89
0.16124
80 -> 88
0.49143
81 -> 89
0.40929
Excited state symmetry could not be determined.
Excited State 31: Singlet-?Sym 5.0777 eV 244.17 nm f=0.0224
77 -> 87
-0.17754
79 -> 89
0.18419
84 -> 94
0.15173
84 -> 96
-0.14481
85 -> 91
0.17438
85 -> 94
0.22614
85 -> 96
0.18506
86 -> 92
0.45863
Excited state symmetry could not be determined.
Excited State 32: Singlet-?Sym 5.1031 eV 242.96 nm f=0.0005
84 -> 92
-0.19513
86 -> 94
0.64967
174
APPENDIX A (continued)
Excited state symmetry could not be determined.
Excited State 33: Singlet-?Sym 5.1076 eV 242.75 nm f=0.0108
77 -> 87
-0.29320
79 -> 89
0.46383
80 -> 88
0.12415
81 -> 89
-0.25832
85 -> 94
-0.14205
86 -> 92
-0.16225
Excited state symmetry could not be determined.
Excited State 34: Singlet-?Sym 5.1602 eV 240.27 nm f=0.0102
79 -> 88
0.12657
80 -> 89
0.60453
82 -> 89
-0.26002
83 -> 89
0.14960
Excited state symmetry could not be determined.
Excited State 35: Singlet-?Sym 5.2224 eV 237.41 nm f=0.0071
77 -> 87
-0.37288
79 -> 89
-0.25647
81 -> 89
0.21340
86 -> 93
0.45003
Excited state symmetry could not be determined.
Excited State 36: Singlet-?Sym 5.3067 eV 233.64 nm f=0.0143
85 -> 94
0.51752
85 -> 95
0.17777
85 -> 96
-0.33694
Excited state symmetry could not be determined.
Excited State 37: Singlet-?Sym 5.3233 eV 232.91 nm f=0.0078
84 -> 92
0.17209
85 -> 97
-0.22521
86 -> 95
-0.28948
86 -> 96
0.51682
Excited state symmetry could not be determined.
Excited State 38: Singlet-?Sym 5.3575 eV 231.42 nm f=0.0845
77 -> 87
-0.10988
84 -> 90
0.13784
84 -> 92
0.24784
84 -> 97
0.17980
85 -> 92
0.26714
175
APPENDIX A (continued)
85 -> 93
85 -> 97
86 -> 93
86 -> 96
0.36245
-0.12793
-0.14226
-0.17594
Excited state symmetry could not be determined.
Excited State 39: Singlet-?Sym 5.3617 eV 231.24 nm f=0.0164
77 -> 87
0.36646
79 -> 89
0.10767
81 -> 89
-0.12028
86 -> 92
0.11307
86 -> 93
0.47495
Excited state symmetry could not be determined.
Excited State 40: Singlet-?Sym 5.3839 eV 230.29 nm f=0.0029
84 -> 90
-0.11369
84 -> 92
-0.19701
84 -> 97
-0.16036
85 -> 93
0.55373
85 -> 97
0.13589
86 -> 96
0.11897
Excited state symmetry could not be determined.
Excited State 41: Singlet-?Sym 5.4549 eV 227.29 nm f=0.0005
80 -> 90
-0.10865
82 -> 90
0.12031
83 -> 90
0.66773
Excited state symmetry could not be determined.
Excited State 42: Singlet-?Sym 5.5280 eV 224.28 nm f=0.0012
80 -> 90
-0.13491
82 -> 90
0.17345
83 -> 90
-0.16991
84 -> 94
0.31921
85 -> 94
-0.14939
85 -> 96
-0.15623
86 -> 97
0.45802
86 -> 98
-0.12887
Excited state symmetry could not be determined.
Excited State 43: Singlet-?Sym 5.5510 eV 223.36 nm f=0.0002
79 -> 90
-0.29418
81 -> 90
0.55832
176
APPENDIX A (continued)
83 -> 91
0.24257
Excited state symmetry could not be determined.
Excited State 44: Singlet-?Sym 5.5724 eV 222.50 nm f=0.0501
78 -> 88
-0.45721
81 -> 90
-0.16248
83 -> 91
0.47215
Excited state symmetry could not be determined.
Excited State 45: Singlet-?Sym 5.5782 eV 222.26 nm f=0.0033
78 -> 88
0.52864
79 -> 90
0.11049
81 -> 90
-0.17393
83 -> 91
0.37355
85 -> 97
-0.11320
Excited state symmetry could not be determined.
Excited State 46: Singlet-?Sym 5.6142 eV 220.84 nm f=0.0061
80 -> 90
-0.36424
82 -> 90
0.49691
83 -> 90
-0.12831
84 -> 94
-0.13847
86 -> 97
-0.21943
Excited state symmetry could not be determined.
Excited State 47: Singlet-?Sym 5.6613 eV 219.00 nm f=0.0113
79 -> 91
-0.23436
81 -> 91
0.43247
84 -> 94
-0.28034
85 -> 95
0.12157
85 -> 96
-0.27586
86 -> 97
0.10411
Excited state symmetry could not be determined.
Excited State 48: Singlet-?Sym 5.6717 eV 218.60 nm f=0.0023
80 -> 91
-0.32695
82 -> 91
0.42425
83 -> 91
-0.22457
85 -> 97
-0.33928
85 -> 98
0.10499
Excited state symmetry could not be determined.
Excited State 49: Singlet-?Sym 5.7295 eV 216.40 nm f=0.0003
177
APPENDIX A (continued)
84 -> 92
84 -> 93
0.18716
0.66669
Excited state symmetry could not be determined.
Excited State 50: Singlet-?Sym 5.7320 eV 216.30 nm f=0.0047
79 -> 91
-0.17843
81 -> 91
0.35822
84 -> 94
0.21127
84 -> 95
-0.18468
84 -> 96
0.37210
84 -> 99
-0.10773
85 -> 95
-0.14399
85 -> 96
0.14189
86 -> 98
0.15687
Pyridine Derivative
Excited State 1: Singlet-?Sym 2.7551 eV 450.01 nm f=0.0023
97 -> 99
0.69786
This state for optimization and/or second-order correction.
Total Energy, E(RPA) = -1272.44161916
Copying the excited state density for this state as the 1-particle RhoCI density.
Excited state symmetry could not be determined.
Excited State 2: Singlet-?Sym 2.8756 eV 431.16 nm f=0.0557
96 -> 99
0.41616
98 -> 99
0.54895
Excited state symmetry could not be determined.
Excited State 3: Singlet-?Sym 2.9395 eV 421.79 nm f=0.0499
96 -> 99
0.56584
98 -> 99
-0.39774
Excited state symmetry could not be determined.
Excited State 4: Singlet-?Sym 3.5353 eV 350.70 nm f=0.0001
92 ->100
-0.12412
93 -> 99
0.10382
94 -> 99
0.66230
Excited state symmetry could not be determined.
Excited State 5: Singlet-?Sym 3.5953 eV 344.85 nm f=0.0032
92 -> 99
0.67118
94 ->100
-0.14035
178
APPENDIX A (continued)
Excited state symmetry could not be determined.
Excited State 6: Singlet-?Sym 3.6902 eV 335.98 nm f=0.0832
95 -> 99
0.47496
98 ->100
-0.49285
Excited state symmetry could not be determined.
Excited State 7: Singlet-?Sym 3.8483 eV 322.18 nm f=0.0720
97 ->100
0.67589
98 ->101
0.13507
Excited state symmetry could not be determined.
Excited State 8: Singlet-?Sym 3.8821 eV 319.38 nm f=0.2007
95 -> 99
0.35583
96 ->100
0.13013
97 ->101
0.33823
98 ->100
0.44669
Excited state symmetry could not be determined.
Excited State 9: Singlet-?Sym 3.9151 eV 316.68 nm f=0.0002
93 -> 99
0.69483
94 -> 99
-0.11423
Excited state symmetry could not be determined.
Excited State 10: Singlet-?Sym 3.9617 eV 312.96 nm f=0.0048
96 ->100
0.68141
97 ->101
-0.12243
Excited state symmetry could not be determined.
Excited State 11: Singlet-?Sym 4.0207 eV 308.36 nm f=0.0315
97 ->100
-0.12345
98 ->101
0.68001
Excited state symmetry could not be determined.
Excited State 12: Singlet-?Sym 4.0798 eV 303.90 nm f=0.2065
95 -> 99
-0.25309
96 ->103
0.10519
97 ->101
0.58002
97 ->102
-0.11658
98 ->100
-0.17570
Excited state symmetry could not be determined.
Excited State 13: Singlet-?Sym 4.1024 eV 302.22 nm f=0.0017
98 ->103
0.68907
179
APPENDIX A (continued)
Excited state symmetry could not be determined.
Excited State 14: Singlet-?Sym 4.1789 eV 296.69 nm f=0.0010
96 ->101
0.19847
97 ->103
0.58587
98 ->102
-0.24926
98 ->104
0.14216
Excited state symmetry could not be determined.
Excited State 15: Singlet-?Sym 4.2061 eV 294.77 nm f=0.0041
92 ->101
0.13816
94 ->100
0.15837
96 ->101
0.62845
97 ->103
-0.19718
Excited state symmetry could not be determined.
Excited State 16: Singlet-?Sym 4.2325 eV 292.94 nm f=0.0068
96 ->103
0.18488
97 ->102
0.59587
97 ->104
-0.30314
Excited state symmetry could not be determined.
Excited State 17: Singlet-?Sym 4.3504 eV 285.00 nm f=0.0004
92 ->100
0.47190
94 ->101
0.47577
Excited state symmetry could not be determined.
Excited State 18: Singlet-?Sym 4.3622 eV 284.22 nm f=0.0016
92 -> 99
0.11505
92 ->101
0.37987
94 ->100
0.45887
96 ->101
-0.21275
96 ->102
0.12921
98 ->102
0.18332
Excited state symmetry could not be determined.
Excited State 19: Singlet-?Sym 4.4062 eV 281.39 nm f=0.0977
92 ->101
-0.12275
94 ->100
-0.15564
96 ->102
0.26881
96 ->104
-0.13912
97 ->103
0.17070
98 ->102
0.54201
180
APPENDIX A (continued)
Excited state symmetry could not be determined.
Excited State 20: Singlet-?Sym 4.4156 eV 280.78 nm f=0.0274
96 ->103
-0.40277
97 ->102
0.33645
97 ->104
0.44414
Excited state symmetry could not be determined.
Excited State 21: Singlet-?Sym 4.5222 eV 274.17 nm f=0.0605
96 ->102
0.58752
96 ->104
-0.19484
97 ->103
-0.12077
98 ->102
-0.26097
98 ->104
-0.10774
Excited state symmetry could not be determined.
Excited State 22: Singlet-?Sym 4.5985 eV 269.62 nm f=0.0038
96 ->102
0.20611
96 ->104
0.48554
97 ->106
-0.12046
98 ->104
0.39621
Excited state symmetry could not be determined.
Excited State 23: Singlet-?Sym 4.6554 eV 266.32 nm f=0.0209
91 -> 99
0.28893
95 ->100
0.58485
96 ->104
0.11596
Excited state symmetry could not be determined.
Excited State 24: Singlet-?Sym 4.7235 eV 262.48 nm f=0.0034
91 -> 99
0.11493
96 ->102
-0.11907
96 ->104
-0.39712
97 ->105
0.16616
97 ->106
-0.25634
97 ->107
-0.15954
98 ->104
0.41550
Excited state symmetry could not be determined.
Excited State 25: Singlet-?Sym 4.7450 eV 261.30 nm f=0.0361
96 ->103
0.35391
96 ->106
-0.13369
97 ->104
0.35252
98 ->105
0.26682
181
APPENDIX A (continued)
98 ->106
98 ->107
-0.27507
-0.16880
Excited state symmetry could not be determined.
Excited State 26: Singlet-?Sym 4.7621 eV 260.36 nm f=0.0528
91 -> 99
0.62704
95 ->100
-0.26829
Excited state symmetry could not be determined.
Excited State 27: Singlet-?Sym 4.8911 eV 253.49 nm f=0.0004
92 ->100
0.47686
94 -> 99
0.11361
94 ->101
-0.47646
Excited state symmetry could not be determined.
Excited State 28: Singlet-?Sym 4.9030 eV 252.88 nm f=0.0003
92 -> 99
-0.10997
92 ->101
0.52367
94 ->100
-0.42623
Excited state symmetry could not be determined.
Excited State 29: Singlet-?Sym 4.9170 eV 252.15 nm f=0.0016
93 ->100
0.69727
Excited state symmetry could not be determined.
Excited State 30: Singlet-?Sym 4.9429 eV 250.83 nm f=0.2276
88 -> 99
0.13852
95 ->101
0.64565
Excited state symmetry could not be determined.
Excited State 31: Singlet-?Sym 4.9917 eV 248.38 nm f=0.0128
93 ->102
-0.14434
96 ->103
-0.13945
96 ->105
-0.29319
96 ->106
0.31314
96 ->107
0.19361
98 ->105
0.40399
98 ->106
-0.15078
98 ->107
-0.10001
Excited state symmetry could not be determined.
Excited State 32: Singlet-?Sym 5.0703 eV 244.53 nm f=0.0040
93 ->101
0.33258
182
APPENDIX A (continued)
93 ->102
96 ->105
96 ->106
98 ->105
98 ->106
98 ->107
-0.21114
0.13866
-0.16568
0.31064
0.36716
0.17431
Excited state symmetry could not be determined.
Excited State 33: Singlet-?Sym 5.1329 eV 241.55 nm f=0.0198
90 -> 99
0.35746
93 ->101
-0.15194
97 ->105
0.52114
97 ->107
0.10749
Excited state symmetry could not be determined.
Excited State 34: Singlet-?Sym 5.1334 eV 241.52 nm f=0.0014
93 ->101
0.58324
93 ->102
0.16305
97 ->105
0.13530
98 ->105
-0.23050
98 ->106
-0.14355
Excited state symmetry could not be determined.
Excited State 35: Singlet-?Sym 5.1754 eV 239.56 nm f=0.0026
90 -> 99
0.51071
97 ->105
-0.37718
97 ->106
-0.13358
97 ->107
0.11268
Excited state symmetry could not be determined.
Excited State 36: Singlet-?Sym 5.1942 eV 238.70 nm f=0.0106
95 ->102
0.69813
Excited state symmetry could not be determined.
Excited State 37: Singlet-?Sym 5.2964 eV 234.09 nm f=0.0108
96 ->105
0.39953
96 ->110
-0.15607
97 ->104
-0.10225
97 ->108
0.44654
98 ->106
-0.16497
98 ->110
0.15455
Excited state symmetry could not be determined.
183
APPENDIX A (continued)
Excited State 38: Singlet-?Sym
89 -> 99
0.68546
5.3500 eV 231.75 nm f=0.0398
Excited state symmetry could not be determined.
Excited State 39: Singlet-?Sym 5.3550 eV 231.53 nm f=0.0084
89 -> 99
-0.10240
95 ->103
0.29711
96 ->108
0.19811
97 ->106
0.30251
97 ->107
0.11531
98 ->108
0.45978
Excited state symmetry could not be determined.
Excited State 40: Singlet-?Sym 5.3586 eV 231.37 nm f=0.0057
96 ->105
-0.36386
96 ->106
-0.24236
96 ->107
-0.12004
96 ->110
0.17323
97 ->108
0.45315
Excited state symmetry could not be determined.
Excited State 41: Singlet-?Sym 5.3708 eV 230.85 nm f=0.0015
95 ->103
0.63495
97 ->106
-0.11712
98 ->108
-0.23884
Excited state symmetry could not be determined.
Excited State 42: Singlet-?Sym 5.4520 eV 227.41 nm f=0.0294
96 ->109
-0.22677
96 ->111
0.17501
97 ->106
-0.25755
97 ->107
-0.11140
98 ->104
-0.11012
98 ->108
0.31500
98 ->109
0.34064
98 ->111
-0.26236
Excited state symmetry could not be determined.
Excited State 43: Singlet-?Sym 5.4815 eV 226.19 nm f=0.0648
91 ->105
-0.12906
93 ->102
-0.25429
94 ->102
0.13055
96 ->106
-0.29589
184
APPENDIX A (continued)
96 ->107
96 ->110
97 ->108
98 ->106
98 ->110
98 ->112
-0.10721
-0.19083
-0.14948
-0.17011
0.35087
-0.10155
Excited state symmetry could not be determined.
Excited State 44: Singlet-?Sym 5.5167 eV 224.74 nm f=0.0002
93 ->102
0.24793
94 ->102
0.30022
96 ->105
-0.15823
96 ->106
-0.15330
96 ->110
-0.13347
97 ->109
-0.24067
97 ->111
0.18013
98 ->105
0.11962
98 ->106
-0.21454
98 ->107
0.26411
98 ->110
-0.13451
Excited state symmetry could not be determined.
Excited State 45: Singlet-?Sym 5.5211 eV 224.56 nm f=0.0051
94 ->102
0.61466
96 ->105
0.11047
96 ->106
0.13701
98 ->106
0.12983
98 ->107
-0.15490
Excited state symmetry could not be determined.
Excited State 46: Singlet-?Sym 5.5518 eV 223.32 nm f=0.0038
90 ->100
0.12127
96 ->105
0.10562
96 ->110
0.18410
97 ->109
0.25213
97 ->111
-0.18883
98 ->106
-0.17078
98 ->107
0.51936
Excited state symmetry could not be determined.
Excited State 47: Singlet-?Sym 5.5835 eV 222.06 nm f=0.0007
92 ->102
0.69518
185
APPENDIX A (continued)
Excited state symmetry could not be determined.
Excited State 48: Singlet-?Sym 5.5887 eV 221.85 nm f=0.0185
91 ->105
0.17672
93 ->102
0.37263
96 ->106
-0.15365
97 ->109
0.28699
97 ->111
-0.21037
98 ->105
0.21624
98 ->106
0.18087
98 ->110
0.17972
Excited state symmetry could not be determined.
Excited State 49: Singlet-?Sym 5.6241 eV 220.45 nm f=0.0219
90 -> 99
-0.14044
97 ->106
-0.29759
97 ->107
0.58373
Excited state symmetry could not be determined.
Excited State 50: Singlet-?Sym 5.6420 eV 219.75 nm f=0.0029
93 ->103
0.68712
94 ->103
-0.14001
TDDFT Triplet State Results
Chloride Derivative
Excited state symmetry could not be determined.
Excited State 1: ?Spin -?Sym 0.0791 eV 15679.83 nm f=0.0001
82B -> 86B
0.87231
83B -> 86B
-0.44770
84B -> 86B
0.29591
Excited state symmetry could not be determined.
Excited State 2: ?Spin -?Sym 0.4574 eV 2710.87 nm f=0.0025
87A -> 89A
0.19078
87A -> 91A
-0.11429
85B -> 86B
0.95921
Excited state symmetry could not be determined.
Excited State 3: ?Spin -?Sym 0.4814 eV 2575.35 nm f=0.0000
81B -> 86B
0.90122
82B -> 86B
-0.27985
186
APPENDIX A (continued)
83B -> 86B
84B -> 86B
-0.31563
0.24256
Excited state symmetry could not be determined.
Excited State 4: ?Spin -?Sym 0.7152 eV 1733.63 nm f=0.0010
83B -> 86B
0.53879
84B -> 86B
0.83478
Excited state symmetry could not be determined.
Excited State 5: ?Spin -?Sym 0.7834 eV 1582.69 nm f=0.0000
81B -> 86B
0.48242
82B -> 86B
0.43302
83B -> 86B
0.64559
84B -> 86B
-0.39422
Excited state symmetry could not be determined.
Excited State 6: ?Spin -?Sym 1.0488 eV 1182.12 nm f=0.0115
87A -> 88A
0.96604
79B -> 86B
0.19736
Pyridine Derivative
Excited state symmetry could not be determined.
Excited State 1: ?Spin -?Sym 0.0849 eV 14605.53 nm f=0.0001
99A ->100A
-0.13424
93B -> 98B
0.14706
94B -> 98B
1.02804
95B -> 98B
0.46736
Excited state symmetry could not be determined.
Excited State 2: ?Spin -?Sym 0.2672 eV 4640.52 nm f=0.0000
93B -> 98B
0.69435
94B -> 98B
-0.38245
95B -> 98B
0.66510
Excited state symmetry could not be determined.
Excited State 3: ?Spin -?Sym 0.3402 eV 3644.48 nm f=0.0000
96B -> 98B
1.00815
Excited state symmetry could not be determined.
Excited State 4: ?Spin -?Sym 0.4290 eV 2889.97 nm f=0.0145
99A ->103A
0.25553
99A ->104A
-0.10813
187
APPENDIX A (continued)
97B -> 98B
0.79691
Excited state symmetry could not be determined.
Excited State 5: ?Spin -?Sym 0.4473 eV 2772.06 nm f=0.0000
93B -> 98B
0.75487
94B -> 98B
0.19871
95B -> 98B
-0.64629
Excited state symmetry could not be determined.
Excited State 6: ?Spin -?Sym 1.0063 eV 1232.04 nm f=0.0083
99A ->100A
0.94620
88B -> 98B
0.12402
90B -> 98B
-0.10050
91B -> 98B
-0.50825
188
APPENDIX A (continued)
Bipyridine Complexes
Cartesian Coordinates from calculations
Chloride Derivative
Atom
Re
C
O
C
O
C
O
Cl
C
C
C
C
H
C
H
C
C
C
H
H
N
N
H
H
C
C
H
H
Coordinates (Angstroms)
X
Y
0.0134
-0.006173
0.002938
-0.001006
0.050246
0.004096
-1.68912
-0.930029
-2.720196 -1.515932
-0.852997
1.707705
-1.383338
2.775631
1.26576
-2.23249
3.847406
1.248679
4.104954
1.734566
2.536345
0.804527
2.794699
1.282012
4.682878
2.0832
1.627645
0.294157
2.349134
1.270705
1.985528
0.191588
-0.515899 -0.568146
-0.215236 -0.693141
-1.481807 -0.864402
-0.96258
-1.089359
2.020288
0.827999
0.379783
-0.084514
4.247424
1.224555
2.973773
0.488341
4.642129
1.717606
1.059909
-0.306779
5.656188
2.057949
1.327695
-0.39529
189
Z
-0.009143
1.927899
3.114015
-0.015717
-0.068154
-0.076131
-0.126694
-0.037423
-1.807158
0.548759
-1.550763
0.744217
1.397744
-2.597962
1.730607
-3.955622
-3.069684
-4.431256
-2.681383
-5.110087
-0.278278
-2.167031
-2.813745
-4.285926
-0.751561
-4.883289
-0.937836
-5.931771
APPENDIX A (continued)
Pyridine Derivative
Atom
Re
C
O
C
O
C
O
C
C
C
C
H
C
H
C
C
C
H
H
N
N
N
C
C
C
H
C
H
C
H
H
H
H
H
C
C
H
H
Coordinates (Angstoms)
X
Y
0.008977
0.008672
0.006403
0.008009
0.057828
0.00514
-1.851329
-0.53913
-2.981936 -0.889822
-0.527216
1.878255
-0.841332
3.01749
3.943866
0.822652
4.317217
1.183707
2.598378
0.51698
2.97191
0.863805
4.948798
1.451386
1.596506
0.217737
2.550591
0.886818
1.892317
0.205874
-0.678126 -0.220901
-0.441823 -0.235608
-1.676653 -0.366612
-1.267096
-0.40172
2.124288
0.528076
0.314907
-0.008627
0.687144
-2.138802
0.084261
-3.053218
1.682672
-2.581207
0.446254
-4.406013
-0.711866 -2.689293
2.097192
-3.918382
2.140337
-1.847086
1.470796
-4.854119
-0.074851 -5.088763
2.885763
-4.214365
1.765765
-5.898905
4.311552
0.811769
2.903051
0.382818
4.814904
1.15585
0.869287
-0.025894
5.852924
1.397242
1.087996
-0.032699
190
Z
-0.00898
1.93073
3.114429
-0.010421
-0.061466
-0.024065
-0.045751
-1.862287
0.502397
-1.584789
0.721881
1.342338
-2.63229
1.719516
-4.00812
-3.094644
-4.474654
-2.700846
-5.158303
-0.292643
-2.183995
-0.053043
-0.870884
0.772656
-0.889104
-1.508143
0.808395
1.423828
-0.035161
-1.551767
1.492034
-0.021919
-2.881077
-4.355071
-0.81354
-4.940483
-1.019211
-6.003599
APPENDIX A (continued)
TDDFT Triplet State Results
Chloride Derivative
Excited state symmetry could not be determined.
Excited State 1: ?Spin -?Sym 0.0710 eV 17452.37 nm f=0.0000
79A -> 82A
-0.11247
76B -> 78B
1.04337
Excited state symmetry could not be determined.
Excited State 2: ?Spin -?Sym 0.5132 eV 2415.68 nm f=0.0000
75B -> 78B
1.02328
Excited state symmetry could not be determined.
Excited State 3: ?Spin -?Sym 0.5413 eV 2290.57 nm f=0.0004
79A -> 81A
0.33379
79A -> 83A
0.12168
77B -> 78B
0.96774
Excited state symmetry could not be determined.
Excited State 4: ?Spin -?Sym 0.7886 eV 1572.27 nm f=0.0005
79A -> 80A
0.99303
Excited state symmetry could not be determined.
Excited State 5: ?Spin -?Sym 1.0040 eV 1234.89 nm f=0.0256
79A -> 81A
0.90751
71B -> 78B
0.12595
77B -> 78B
-0.19337
Excited state symmetry could not be determined.
Excited State 6: ?Spin -?Sym 1.0347 eV 1198.28 nm f=0.0010
79A -> 82A
0.33981
69B -> 78B
-0.11391
70B -> 78B
-0.13905
73B -> 78B
0.93687
Pyridine Derivative
Excited state symmetry could not be determined.
Excited State 1: ?Spin -?Sym 0.0536 eV 23122.53 nm f=0.0001
91A -> 95A
0.23091
82B -> 90B
0.10232
87B -> 90B
0.11545
191
APPENDIX A (continued)
88B -> 90B
1.31894
Excited state symmetry could not be determined.
Excited State 2: ?Spin -?Sym 0.3409 eV 3636.44 nm f=0.0000
87B -> 90B
1.04080
Excited state symmetry could not be determined.
Excited State 3: ?Spin -?Sym 0.3774 eV 3285.59 nm f=0.0064
91A -> 94A
0.40443
91A -> 96A
-0.14715
89B -> 90B
0.91107
Excited state symmetry could not be determined.
Excited State 4: ?Spin -?Sym 0.9083 eV 1365.05 nm f=0.0002
91A -> 92A
0.99159
91A -> 96A
-0.13277
Excited state symmetry could not be determined.
Excited State 5: ?Spin -?Sym 0.9668 eV 1282.43 nm f=0.0003
91A -> 93A
0.99322
91A -> 95A
0.12202
Excited state symmetry could not be determined.
Excited State 6: ?Spin -?Sym 1.1709 eV 1058.91 nm f=0.0072
91A -> 93A
-0.11479
91A -> 95A
0.88273
91A -> 97A
0.30482
83B -> 90B
-0.22091
85B -> 90B
-0.42984
192
APPENDIX A (continued)
Bipyrimidine Complexes
Cartesian Coordinates from calculations
Chloride Derivative
Atom
Re
C
O
C
O
C
O
Cl
C
C
C
H
C
H
C
C
H
H
N
N
C
C
H
H
N
N
Coordinates (Angstroms)
X
Y
-0.010421 -0.001309
-0.01628
0.001068
0.033676
0.002413
-1.709715 -0.933264
-2.73583 -1.525209
-0.888807 1.709739
-1.427698 2.772216
1.247312 -2.219419
4.105358
1.711916
2.513996
0.814267
2.800008
1.279797
4.744364
2.062007
1.602729
0.302451
2.387632
1.278246
-0.510962 -0.571923
-0.14618 -0.676182
-1.48529 -0.883274
-0.838231 -1.074191
1.99388
0.832164
0.356648 -0.080126
4.55055
1.667687
1.147949 -0.252417
5.548871
1.986368
1.505436 -0.301844
3.755872
1.221605
2.01659
0.236429
193
Z
0.009247
1.94728
3.132000
0.001343
-0.050409
-0.049357
-0.092597
-0.023862
0.480408
-1.532976
0.741694
1.282304
-2.583223
1.742784
-3.072898
-4.420229
-2.718034
-5.152753
-0.260422
-2.145852
-0.854876
-4.778815
-1.138242
-5.80266
-1.856088
-3.862593
APPENDIX A (continued)
Pyridine Derivative
Atom
Re
C
O
C
O
C
O
C
C
C
H
C
H
C
C
H
H
N
N
N
C
C
C
H
C
H
C
H
H
H
C
C
H
H
N
N
Coordinates (Angstoms)
X
Y
-0.015979
0.00033
-0.01307 -0.008871
0.039591 -0.016517
-1.875613 -0.553713
-3.004627 -0.905569
-0.565005 1.868958
-0.88866
3.004705
4.303108
1.209137
2.581416
0.485524
2.96788
0.905966
4.98683
1.515725
1.576921
0.183881
2.577831
0.967182
-0.681493 -0.182058
-0.3698
-0.191398
-1.699063 -0.303394
-1.145301 -0.321328
2.096422
0.530301
0.288301 -0.007183
0.671699 -2.142412
0.069007 -3.057357
1.679214 -2.582162
0.44508
-4.405806
-0.739433 -2.698056
2.10812
-3.914943
2.134744 -1.849795
1.483878 -4.849881
-0.075028 -5.088609
2.906924 -4.208543
1.791718 -5.890977
4.718201
1.098051
0.983268
-0.028658
5.740573
1.296475
1.309511
-0.044898
3.853658
0.744218
1.94648
0.165883
194
Z
0.016531
1.957407
3.139808
0.01019
-0.041645
0.016503
0.006979
0.424903
-1.553752
0.717251
1.207606
-2.605514
1.726395
-3.104008
-4.468961
-2.751852
-5.214509
-0.265315
-2.158111
-0.039449
-0.857668
0.773807
-0.891095
-1.482194
0.79394
1.428722
-0.052268
-1.554419
1.466594
-0.052769
-0.917864
-4.829892
-1.223169
-5.864855
-1.899333
-3.896954
APPENDIX A (continued)
TDDFT Triplet State Results
Chloride Derivative
Excited state symmetry could not be determined.
Excited State 1: ?Spin -?Sym 0.0804 eV 15421.53 nm f=0.0000
79A -> 82A
-0.10265
75B -> 78B
-0.22629
76B -> 78B
0.99921
Excited state symmetry could not be determined.
Excited State 2: ?Spin -?Sym 0.4846 eV 2558.38 nm f=0.0000
73B -> 78B
0.81206
75B -> 78B
-0.61123
76B -> 78B
-0.12706
Excited state symmetry could not be determined.
Excited State 3: ?Spin -?Sym 0.5898 eV 2102.04 nm f=0.0016
79A -> 81A
-0.20714
79A -> 83A
-0.10854
77B -> 78B
0.97843
Excited state symmetry could not be determined.
Excited State 4: ?Spin -?Sym 0.8508 eV 1457.25 nm f=0.0018
79A -> 81A
0.61642
79A -> 83A
0.48888
72B -> 78B
0.10678
74B -> 78B
0.65486
Excited state symmetry could not be determined.
Excited State 5: ?Spin -?Sym 0.9055 eV 1369.29 nm f=0.0022
79A -> 80A
0.96276
79A -> 82A
-0.23968
75B -> 78B
0.10605
Excited state symmetry could not be determined.
Excited State 6: ?Spin -?Sym 0.9791 eV 1266.27 nm f=0.0009
79A -> 82A
0.12351
79A -> 83A
0.13758
71B -> 78B
0.34344
73B -> 78B
0.57447
74B -> 78B
-0.11233
75B -> 78B
0.68605
195
APPENDIX A (continued)
76B -> 78B
0.15125
Pyridine Derivative
Excited state symmetry could not be determined.
Excited State 1: ?Spin -?Sym 0.0204 eV 60649.36 nm f=0.0000
91A -> 95A
0.37574
80B -> 90B
0.17662
85B -> 90B
0.22779
86B -> 90B
-1.02853
87B -> 90B
1.63615
88B -> 90B
0.22900
Excited state symmetry could not be determined.
Excited State 2: ?Spin -?Sym 0.1384 eV 8955.44 nm f=0.0004
91A -> 94A
0.11111
89B -> 90B
0.97446
Excited state symmetry could not be determined.
Excited State 3: ?Spin -?Sym 0.2396 eV 5173.85 nm f=0.0000
85B -> 90B
0.76574
87B -> 90B
-0.12693
88B -> 90B
0.70505
Excited state symmetry could not be determined.
Excited State 4: ?Spin -?Sym 0.5831 eV 2126.40 nm f=0.0001
85B -> 90B
-0.71559
88B -> 90B
0.70751
Excited state symmetry could not be determined.
Excited State 5: ?Spin -?Sym 0.6619 eV 1873.19 nm f=0.0039
91A -> 94A
0.59242
91A -> 96A
-0.12826
86B -> 90B
0.76512
87B -> 90B
0.47986
Excited state symmetry could not be determined.
Excited State 6: ?Spin -?Sym 0.8603 eV 1441.18 nm f=0.0006
91A -> 92A
0.76872
91A -> 93A
0.62413
91A -> 95A
0.13788
196
APPENDIX A (continued)
Bond Length Comparison (Å)
Bond
Re-NL
Re-NL
Re-CAx
Re-CEq
Re-CEq
Re-Cl
Re(CO)3(Bpy)Cl
2.190
2.190
1.922
1.937
1.937
2.555
Re(CO)3(Bpm)Cl
2.188
2.187
1.924
1.938
1.938
2.550
Re(CO)3(Bpz)Cl
2.178
2.178
1.927
1.942
1.942
2.550
Re(CO)3(MeBpz)Cl
2.181
2.181
1.925
1.940
1.940
2.550
Re-NL
Re-NL
Re-NPy
Re-CAx
Re-CEq
Re-CEq
Re(CO)3(Bpy)(Py)+
2.196
2.197
2.252
1.945
1.939
1.940
Re(CO)3(Bpm)(Py)+
2.196
2.196
2.251
1.948
1.940
1.941
Re(CO)3(Bpz)(Py)+
2.189
2.189
2.250
1.951
1.944
1.944
Re(CO)3(MeBpz)(Py)+
2.191
2.191
2.251
1.949
1.943
1.943
Calculated CO stretching frequencies for all compexes (Unscaled, cm-1)
Re(CO)3(Bpy)Cl
1977.1
1897.1
1872.8
Re(CO)3(Bpm)Cl
1982.1
1905.0
1879.8
Re(CO)3(Bpz)Cl
1984.4
1911.2
1886.0
Re(CO)3(MeBpz)Cl
1981.6
1906.5
1881.7
Re(CO)3(Bpy)(Py)+
1997.9
1919.1
1908.1
Re(CO)3(Bpm)(Py)+
2002.0
1925.1
1915.3
Re(CO)3(Bpz)(Py)+
2004.4
1931.1
1920.5
Re(CO)3(MeBpz)(Py)+
2001.7
1920.7
1916.3
197
APPENDIX A (continued)
Frontier Orbitals
A = Re/CO/Cl, B = Re/CO, C = Re/Cl, L = Ligand (Bipyrazine or Me-Bipyrazine), Py =
Pyridine
Chloride Derivatives
B (+8)
0
Re (+7)
CO (+6)
L (+5)
B (+3)
-2
L (+2)
B (+8)
Re (+7)
CO (+6)
B (+4)
L (+5)
B (+3)
B (+4)
Re (+7)
CO (+6)
B (+7)
CO (+6)
L (+5)
L (+5)
B (+3)
B (+4)
B (+3)
B (+4)
L (+1)
L (+2)
L (+1)
L (L)
Energy (eV)
B (+8)
B (+8)
L (+2)
L (+2)
L (+1)
L (+1)
L (L)
L (L)
L (L)
-4
Gap = 2.80
Gap = 2.65
Gap = 2.65
Gap = 2.53
-6
A (H)
A (-1)
A (H)
A (-1)
B (-2)
A (-3)
B (-2)
A (-4)
A (-3)
Cl (-5)
L (-6)
-8
A (H)
L (-7)
A (H)
L (-6)
L (-8)
A (-3)
A (-1)
B (-2)
B (-2)
A (-4)
Cl (-5)
A (-1)
A (-4)
A (-5)
L (-6) L (-8) L (-7)
C (-3)
C (-4)
Cl (-5) L (-6)
L (-7) L (-8)
L (-7) L (-8)
-10
Re(CO)3(Bpy)Cl
Re(CO)3(Bpm)Cl
198
Re(CO)3(Bpz)Cl
Re(CO)3(MeBpz)Cl
APPENDIX A (continued)
Pyridine Derivatives
-4
CO (+8)
L (+7)
B (+6)
Py (+5)
B (+4)
Py (+3)L (+2)
CO (+8)
L (+7)
B (+6)
Py (+5)
L (+1)
-6
L (+7)
Py (+5)
B (+4)
Py (+3)
L (+2)
CO (+8)
L (+7)
B (+6)
B P(+5)
B (+4)
CO (+8)
B (+6)
B (+4)
Py (+3)
L (+2)
L (+1)
Py (+3)
L (+1)
L (+2)
L (+1)
L (L)
L (L)
L (L)
Energy (eV)
L (L)
-8
Gap = 3.46
Gap = 3.33
Gap = 3.31
Gap = 3.18
B (H)
B (-2)
B (-1)
B (H)
-10
L (-3)
B (-2)
B (H)
L Py (-5)
L Py (-5)
L (-3)
L Py (-5)
L (-4)
L Py (-6)
Py (-7)
L Py (-6)
Py (-7)Py (-8)
+
B (-1)
B (-1)
B (-2)
B (H)
Py (-6)
Py (-7)
L (-8)
Py (-8)
+
Re(CO)3(Bpm)(Py)
199
L (-4)
L Py (-6)
Py (-7)
Py (-8)
Re(CO)3(Bpy)(Py)
B (-2)
L (-4) L (-3) L (-5)
L (-3)
L (-4)
-12
B (-1)
+
Re(CO)3(Bpz)(Py)
+
Re(CO)3(MeBpz)(Py)
APPENDIX A (continued)
Emission Data
Chloride Derivatives - Triplet Transitions
29
3
LMLCT
3
LLCT
28
27
3
LMLCT
3
LLCT
26
3
LLCT
3
3
LLCT
3
LLCT
LMLCT
25
3
LMLCT
LMLCT
3
24
MLMLCT
3
LMLCT
3
LMLCT
3
MLMLCT
3
LMLCT
3
23
3
-1
3
Energy (cm x 10 )
3
LMLCT
LMLCT
22
21
3
3
LMLCT
MLMLCT
3
MLMLCT
3
MLMLCT
3
MLLCT
20
3
MLMLCT
19
3
3
MLLCT
MLMLCT
3
18
MLLCT
3
MLMLCT
3
17
0.15
0.10
0.05
0.00
MLLCT
1
G.S.
Re(CO)3(bpy)Cl
1
G.S.
Re(CO)3(bpm)Cl
G.S.
Re(CO)3(bpz)Cl
Complex
200
1
1
G.S.
Re(CO)3(mebpz)Cl
APPENDIX A (continued)
Pyridine Derivatives - Triplet Transitions
34
3
33
ILCT
32
3
31
3
LLCT
ILCT
3
30
3
LLCT
3
LLCT
LLCT
-1
3
Energy (cm x 10 )
29
3
28
3
27
3
3
26
MLMLCT
LMLCT
3
25
24
LMLCT
MLMLCT
3
3
3
MLMLCT
3
MLLCT
23
MLMLCT
3
3
3
LMLCT
3
MLLCT
3
3
3
LMCT
LMCT
3
1
1
G.S.
Re(CO)3(bpy)(py)
+
MLLCT
1
G.S.
Re(CO)3(bpm)(py)
+
MLLCT
3
MLCT
MLLCT
dd
1
G.S.
Re(CO)3(bpz)(py)
Complex
201
3
MLCT
MLCT
3
21
20
0.15
0.10
0.05
0.00
LMCT
3
dd
MLMLCT
22
3
MLMLCT
+
G.S.
Re(CO)3(mebpz)(py)
+
APPENDIX A (continued)
Detailed Triplet Transitions
State
f
Re(CO)3(Bpy)Cl
Singlet to Triplet
1
0.000
2
0.000
3
0.000
4
0.001
5
0.026
6
0.001
Re(CO)3(Bpm)Cl
Singlet to Triplet
1
0.000
2
0.000
3
0.002
4
0.002
Ψ0→ΨV
H-3
H-4
H-2
H
H
H-6
→
→
→
→
→
→
H-1
H-1
H-1
L
L+1
H-1
%
type
EVER
1.0
1.0
0.9
1.0
0.9
0.9
MLLCT
Re,CO,Cl
Re,CO
L
L
L
L,Cl
20.0
20.5
24.1
24.3
26.3
28.1
28.3
→
→
→
→
→
→
→
Re,CO,Cl
Re,CO,Cl
Re,CO,Cl
Re,CO,L
Re,CO,Cl
CO
Re,CO,Cl
→
→
→
→
→
→
Re,CO,Cl
Re,CO,Cl
Re,CO,Cl
CO
CO
Re,CO,Cl
0.002
0.001
H-3
H-6
H-2
H
H-5
H
H-4
→
→
→
→
→
→
→
H-1
H-1
H-1
L+1
H-1
L
H-1
0.9
0.6
0.9
0.4
0.4
0.9
0.9
MLLCT
Re,CO,Cl
Re,CO
L
L
L
L
CO,L
Re(CO)3(Bpz)Cl
Singlet to Triplet
1
0.000
2
0.000
3
0.001
4
0.001
5
0.000
6
0.011
H-5
H-6
H-4
H-3
H-2
H
→
→
→
→
→
→
H-1
H-1
H-1
H-1
H-1
L
0.8
0.8
0.9
0.8
0.6
0.9
MLLCT
Re,CO,Cl
Re,CO
L
L
L
L
→
→
→
→
→
→
Re,CO,Cl
Re,CO,Cl
Re,CO,Cl
Re,CO,Cl
Re,CO,Cl
CO
H-5 → H-1
H-2 → H-1
H-6 → H-1
H-3 → H-1
H-4 → H-1
H
→ L
Ψ0→ΨV
0.7
0.9
0.8
0.7
0.4
1.0
MLLCT
del
L
Re,CO
L
L
L
%
type
→
→
→
→
→
→
Re,CO,Cl
Re,CO,Cl
Re,CO,Cl
Re,CO,Cl
Re,CO,Cl
CO,L
5
6
Re(CO)3(MeBpz)Cl
Singlet to Triplet
1
0.000
2
0.003
3
0.000
4
0.001
5
0.000
6
0.012
State
f
Re(CO)3(Bpy)(Py)+
Singlet to Triplet
1
0.000
H-3
→
H-1
202
1.0
MLLCT
Re,CO
→
18.8
19.4
22.7
23.5
25.6
26.1
26.7
17.1
17.7
20.9
22.7
22.9
23.4
26.0
18.1
18.7
21.8
22.0
23.9
24.4
26.6
EVER
23.4
Re,CO,L 23.9
APPENDIX A (continued)
H-4
H-2
H
H
H
→
→
→
→
→
H-1
H-1
L
L+1
L+3
1.0
0.8
1.0
1.0
0.7
Re,CO
L
L
L
L
→
→
→
→
→
Re,CO,L
Re,CO,L
L
Py
L
H-4
H-2
H-6
H-3
H-6
H-3
H-5
H
→
→
→
→
→
→
→
→
H-1
H-1
H-1
H-1
H-1
H-1
H-1
L
0.7
1
0.5
0.5
0.5
0.5
0.5
0.6
MLLCT
Re,CO,L
L
Re,CO
L
Re,CO
L
L
L
→
→
→
→
→
→
→
→
Re,CO,L
Re,CO,L
Re,CO,L
Re,CO,L
Re,CO,L
Re,CO,L
Re,CO,L
Py,CO
H-5
H-3
H-2
H-6
H-4
H
→
→
→
→
→
→
H-1
H-1
H-1
H-1
H-1
L
0.7
0.6
1.0
0.9
0.9
0.9
MLLCT
Re,CO
L
L
Re,CO
L
L
→
→
→
→
→
→
Re,CO
Re,CO
Re,CO
Re,CO
Re,CO
CO
Re(CO)3(MeBpz)(Py)+
Singlet to Triplet
1
0.000
H-5
2
0.000
H-6
H-4
3
0.000
H-3
4
0.015
H-2
5
0.000
H-6
H-4
6
0.008
H
→
→
→
→
→
→
→
→
H-1
H-1
H-1
H-1
H-1
H-1
H-1
L
0.8
0.5
0.5
1.0
0.9
0.6
0.4
0.8
MLLCT
Re,CO
Re,CO
L
L
Re,L
Re,CO
L
L
→
→
→
→
→
→
→
→
Re,L
Re,L
Re,L
Re,L
Re,L
Re,L
Re,L
L
2
3
4
5
6
0.000
0.006
0.000
0.000
0.007
Re(CO)3(Bpm)(Py)+
Singlet to Triplet
1
0.000
2
0.000
3
0.000
4
0.000
5
6
0.004
0.001
Re(CO)3(Bpz)(Py)+
Singlet to Triplet
1
0.000
2
0.000
3
0.000
4
0.000
5
0.007
6
0.005
203
26.2
26.5
30.8
31.2
32.9
22.6
22.7
23.7
24.5
27.3
27.9
29.5
21.0
20.8
22.2
22.3
23.7
24.3
29.9
21.4
22.1
23.6
24.2
24.9
25.0
29.6
APPENDIX A (continued)
Scaling Curves
IR Scaling Curves
IR Data Correction Curve
2060.0
y = 1.23x - 420.92
R2 = 0.95
2040.0
Experimental IR Stretch
2020.0
2000.0
1980.0
1960.0
1940.0
1920.0
1900.0
1880.0
1860.0
1880.0
1900.0
1920.0
1940.0
1960.0
1980.0
2000.0
Calculated IR Stretch
Absorption Scaling Curve
Absorption Correction Curve
430
Experimental Abs. Band
420
y = 0.7829x + 46.171
R2 = 0.9939
410
400
390
380
370
410
420
430
440
450
Calculated Abs. Band
204
460
470
480
2020.0
APPENDIX A (continued)
Emission Scaling Curves (Top: Chloride Derivatives, Bottom: Pyridine Derivatives)
Correction Curve for Chloride Derivatives
590
580
y = 0.5516x + 210.78
R2 = 0.9232
570
Caclculated emission
560
550
540
530
520
510
500
490
500
520
540
560
580
600
620
640
660
680
Experimental Emission
Correction Curve for Pyridine Derivatives
490
480
y = 0.3641x + 246.32
R2 = 0.9812
Calculated Emission
470
460
450
440
430
420
450
470
490
510
530
550
570
Experimental Emission
205
590
610
630
650
APPENDIX A (continued)
Crystal Structure Reports
Re(CO)3(bpz)Cl
Atomic coordinates (x 104) and equivalent isotropic displacementparameters(Ǻ2 x 103)
U(eq) is defined as one third of the trace of the orthogonalized Uij tensor.
______________________________________________________
x
y
z
U(eq)
______________________________________________________
C(1)
1291(4)
2541(4)
735(2)
21(1)
C(2)
5490(3)
4364(4)
1181(1)
19(1)
C(3)
4100(3)
231(4)
1127(2)
19(1)
C(4)
-783(3)
-54(3)
2274(2)
19(1)
C(5)
-2019(3)
-960(3)
2867(2)
21(1)
C(6)
716(4)
190(4)
3956(2)
21(1)
C(7)
1980(3)
1144(3)
3383(1)
16(1)
C(8)
4204(3)
2263(3)
3635(1)
16(1)
C(9)
5267(4)
2570(4)
4481(2)
21(1)
C(10)
8275(4)
4279(4)
4016(2)
21(1)
C(11)
7269(3)
3991(3)
3166(2)
18(1)
Cl(1)
2396(1)
5979(1)
2627(1)
22(1)
N(1)
1216(3)
1049(3)
2533(1)
16(1)
N(2)
5218(3)
2999(3)
2972(1)
15(1)
N(3)
-1299(3)
-832(3)
3715(1)
23(1)
N(4)
7302(3)
3588(3)
4682(1)
24(1)
O(1)
54(3)
2403(3)
153(1)
32(1)
O(2)
6845(3)
5307(3)
872(1)
28(1)
O(3)
4625(3)
-1252(3)
767(1)
30(1)
Re(1)
3325(1)
2745(1)
1739(1)
14(1)
206
APPENDIX A (continued)
Anisotropic displacement parameters (Ǻ2 x 103)
The anisotropic displacement factor exponent takes the form:
-2 2 [ h2 a*2 U11 + ... + 2 h k a* b* U12 ]
______________________________________________
U11 U22 U33 U23 U13 U12
______________________________________________
C(1) 19(1) 22(1) 22(1) 6(1) 4(1) 3(1)
C(2) 19(1) 20(1) 16(1) 2(1) 2(1) 6(1)
C(3) 18(1) 23(1) 16(1) 5(1) -2(1) 2(1)
C(4) 16(1) 20(1) 21(1) 3(1) 0(1) 2(1)
C(5) 13(1) 16(1) 31(1) 3(1) 2(1) 0(1)
C(6) 19(1) 24(1) 21(1) 7(1) 5(1) 4(1)
C(7) 15(1) 16(1) 18(1) 2(1) 3(1) 5(1)
C(8) 14(1) 17(1) 18(1) 4(1) 4(1) 4(1)
C(9) 21(1) 24(1) 17(1) 5(1) 2(1) 4(1)
C(10) 16(1) 21(1) 24(1) 2(1) -1(1) 2(1)
C(11) 14(1) 17(1) 23(1) 4(1) 3(1) 2(1)
Cl(1) 19(1) 18(1) 28(1) 4(1) 8(1) 4(1)
N(1) 13(1) 14(1) 19(1) 2(1) 2(1) 2(1)
N(2) 14(1) 14(1) 16(1) 1(1) 3(1) 3(1)
N(3) 19(1) 22(1) 28(1) 8(1) 8(1) 2(1)
N(4) 21(1) 28(1) 21(1) 3(1) -2(1) 4(1)
O(1) 26(1) 39(1) 31(1) 12(1) -9(1) 3(1)
O(2) 26(1) 30(1) 30(1) 12(1) 12(1) 1(1)
O(3) 38(1) 27(1) 27(1) 2(1) 4(1) 14(1)
Re(1) 12(1) 16(1) 13(1) 3(1) 2(1) 1(1)
______________________________________________
207
APPENDIX A (continued)
Bond lengths [Ǻ]
____________________
C(1)-O(1)
1.143(3)
C(1)-Re(1)
1.936(2)
C(2)-O(2)
1.147(3)
C(2)-Re(1)
1.926(2)
C(3)-O(3)
1.147(3)
C(3)-Re(1)
1.909(2)
C(4)-N(1)
1.343(3)
C(4)-C(5)
1.385(3)
C(4)-H(4)
0.9300
C(5)-N(3)
1.334(3)
C(5)-H(5)
0.9300
C(6)-N(3)
1.335(3)
C(6)-C(7)
1.383(3)
C(6)-H(6)
0.9300
C(7)-N(1)
1.351(3)
C(7)-C(8)
1.469(3)
C(8)-N(2)
1.352(3)
C(8)-C(9)
1.389(3)
C(9)-N(4)
1.339(3)
C(9)-H(9)
0.9300
C(10)-N(4) 1.333(3)
C(10)-C(11) 1.381(3)
C(10)-H(10) 0.9300
C(11)-N(2) 1.343(3)
C(11)-H(11) 0.9300
Cl(1)-Re(1) 2.4899(5)
N(1)-Re(1) 2.1620(18)
N(2)-Re(1) 2.1524(18)
_____________________
208
APPENDIX A (continued)
Bond angles [deg]
___________________________
O(1)-C(1)-Re(1)
178.5(2)
O(2)-C(2)-Re(1)
177.0(2)
O(3)-C(3)-Re(1)
178.0(2)
N(1)-C(4)-C(5)
121.2(2)
N(1)-C(4)-H(4)
119.4
C(5)-C(4)-H(4)
119.4
N(3)-C(5)-C(4)
122.6(2)
N(3)-C(5)-H(5)
118.7
C(4)-C(5)-H(5)
118.7
N(3)-C(6)-C(7)
123.0(2)
N(3)-C(6)-H(6)
118.5
C(7)-C(6)-H(6)
118.5
N(1)-C(7)-C(6)
120.67(19)
N(1)-C(7)-C(8)
115.64(18)
C(6)-C(7)-C(8)
123.7(2)
N(2)-C(8)-C(9)
120.26(19)
N(2)-C(8)-C(7)
115.28(19)
C(9)-C(8)-C(7)
124.5(2)
N(4)-C(9)-C(8)
122.7(2)
N(4)-C(9)-H(9)
118.7
C(8)-C(9)-H(9)
118.7
N(4)-C(10)-C(11)
122.8(2)
N(4)-C(10)-H(10)
118.6
C(11)-C(10)-H(10) 118.6
N(2)-C(11)-C(10)
120.9(2)
N(2)-C(11)-H(11)
119.6
C(10)-C(11)-H(11) 119.6
C(4)-N(1)-C(7)
116.74(19)
C(4)-N(1)-Re(1)
126.80(15)
C(7)-N(1)-Re(1)
116.45(13)
C(11)-N(2)-C(8)
117.34(18)
C(11)-N(2)-Re(1)
125.53(15)
C(8)-N(2)-Re(1)
116.84(14)
C(5)-N(3)-C(6)
115.80(19)
C(10)-N(4)-C(9)
116.0(2)
C(3)-Re(1)-C(2)
88.16(9)
C(3)-Re(1)-C(1)
90.42(9)
C(2)-Re(1)-C(1)
89.91(9)
C(3)-Re(1)-N(2)
94.53(8)
C(2)-Re(1)-N(2)
96.74(8)
C(1)-Re(1)-N(2)
171.82(8)
209
APPENDIX A (continued)
C(3)-Re(1)-N(1)
93.17(8)
C(2)-Re(1)-N(1)
171.87(8)
C(1)-Re(1)-N(1)
98.09(8)
N(2)-Re(1)-N(1)
75.17(7)
C(3)-Re(1)-Cl(1)
176.45(7)
C(2)-Re(1)-Cl(1)
93.26(7)
C(1)-Re(1)-Cl(1)
92.83(7)
N(2)-Re(1)-Cl(1)
82.07(5)
N(1)-Re(1)-Cl(1)
84.96(5)
____________________________
[Re(CO)3(bpz)(py)]PF6
Atomic coordinates (x 104) and equivalent isotropic displacement parameters(Ǻ2 x 103)
U(eq) is defined as one third of the trace of the orthogonalized Uij tensor.
_____________________________________________________________
x
y
z
U(eq)
_____________________________________________________________
C(1)
-1542(4)
-305(3)
2244(2)
25(1)
C(2)
553(3)
-2522(3)
2149(2)
27(1)
C(3)
263(3)
-1468(3)
3848(2)
22(1)
C(4)
419(4)
2885(3)
3536(2)
27(1)
C(5)
1006(4)
4366(3)
3934(2)
30(1)
C(6)
3634(4)
3749(3)
4186(2)
29(1)
C(7)
3095(3)
2246(3)
3813(2)
22(1)
C(8)
4185(3)
1014(3)
3785(2)
22(1)
C(9)
5874(3)
1169(3)
4195(2)
26(1)
C(10)
6040(3)
-1357(3)
3777(2)
28(1)
C(11)
4360(3)
-1546(3)
3356(2)
26(1)
C(12)
874(4)
2094(4)
1249(2)
40(1)
C(13)
1308(5)
2880(5)
509(3)
51(1)
C(14)
2329(5)
2212(5)
37(3)
49(1)
C(15)
2854(5)
809(5)
309(3)
46(1)
C(16)
2399(4)
73(4)
1065(2)
38(1)
F(1)
5266(3)
4616(3)
1098(2)
57(1)
F(2)
5211(3)
2823(2)
2215(2)
52(1)
F(3)
7634(3)
3853(3)
1958(2)
56(1)
F(4)
6916(3)
4466(3)
3317(2)
64(1)
F(5)
6946(3)
6275(3)
2204(2)
72(1)
F(6)
4525(3)
5217(3)
2450(2)
61(1)
N(1)
1455(3)
1818(3)
3464(2)
21(1)
N(2)
3423(3)
-364(3)
3363(2)
21(1)
210
APPENDIX A (continued)
N(3)
N(4)
N(5)
O(1)
O(2)
O(3)
O(101)
P(1)
Re(1)
1441(3)
704(3)
1550(2)
28(1)
2612(3)
4827(3)
4253(2)
32(1)
6811(3)
-7(3)
4203(2)
30(1)
-2915(2)
-177(3)
1940(2)
33(1)
490(3)
-3744(3)
1799(2)
39(1)
-69(3)
-2105(2)
4479(2)
30(1)
3150(14)
6964(15)
237(7)
155(5)
6077(1)
4552(1)
2202(1)
31(1)
785(1)
-477(1)
2765(1)
20(1)
___________________________________________________________
Anisotropic displacement parameters (Ǻ2 x 103)
The anisotropic displacement factor exponent takes the form:
-2 π2 [ h2 a*2 U11 + ... + 2 h k a* b* U12 ]
____________________________________________________________________
U11
U22
U33
U23
U13
____________________________________________________________________
C(1)
28(2)
24(1)
23(1)
1(1)
7(1)
C(2)
24(1)
29(2)
27(2)
-2(1)
7(1)
C(3)
17(1)
19(1)
28(2)
-4(1)
1(1)
C(4)
27(1)
23(1)
31(2)
3(1)
9(1)
C(5)
35(2)
23(1)
33(2)
2(1)
12(1)
C(6)
29(2)
25(2)
31(2)
-2(1)
6(1)
C(7)
24(1)
22(1)
20(1)
2(1)
5(1)
C(8)
23(1)
23(1)
19(1)
1(1)
6(1)
C(9)
24(1)
26(1)
28(2)
-1(1)
5(1)
C(10)
26(1)
28(2)
31(2)
2(1)
10(1)
C(11)
28(1)
23(1)
29(2)
-2(1)
10(1)
C(12)
49(2)
39(2)
34(2)
5(1)
13(2)
C(13)
64(3)
48(2)
40(2)
10(2)
10(2)
C(14)
46(2)
66(3)
32(2)
6(2)
8(2)
C(15)
45(2)
62(2)
36(2)
3(2)
19(2)
C(16)
40(2)
43(2)
34(2)
3(1)
13(1)
F(1)
56(1)
73(2)
40(1)
15(1)
4(1)
F(2)
70(2)
32(1)
57(1)
0(1)
24(1)
F(3)
45(1)
73(2)
56(1)
11(1)
21(1)
F(4)
53(1)
99(2)
33(1)
-2(1)
6(1)
F(5)
94(2)
38(1)
90(2)
-9(1)
45(2)
F(6)
59(1)
50(1)
88(2)
4(1)
38(1)
N(1)
23(1)
20(1)
19(1)
3(1)
5(1)
N(2)
19(1)
24(1)
21(1)
0(1)
6(1)
N(3)
25(1)
33(1)
23(1)
-2(1)
4(1)
N(4)
36(1)
23(1)
37(2)
-2(1)
11(1)
211
U12
-2(1)
-2(1)
3(1)
3(1)
6(1)
-2(1)
-2(1)
-2(1)
-2(1)
7(1)
2(1)
7(2)
4(2)
-8(2)
4(2)
7(2)
7(1)
-7(1)
20(1)
-10(1)
-26(1)
19(1)
0(1)
0(1)
-4(1)
0(1)
APPENDIX A (continued)
N(5)
24(1)
34(1)
31(1)
1(1)
6(1)
2(1)
O(1)
24(1)
39(1)
35(1)
2(1)
2(1)
4(1)
O(2)
41(1)
29(1)
45(1)
-12(1)
11(1)
0(1)
O(3)
33(1)
29(1)
29(1)
8(1)
11(1)
1(1)
O(101)
152(9)
227(12)
121(8)
73(8)
59(7)
127(9)
P(1)
32(1)
27(1)
34(1)
2(1)
9(1)
-1(1)
Re(1)
19(1)
20(1)
21(1)
-1(1)
4(1)
-1(1)
_____________________________________________________________________
Bond lengths [Ǻ]
___________________________________________________________________________
C(1)-O(1)
1.144(3)
C(11)-N(2)
1.340(4)
C(1)-Re(1)
1.934(3)
C(11)-H(11)
0.9300
C(2)-O(2)
1.148(4)
C(12)-N(3)
1.360(4)
C(2)-Re(1)
1.927(3)
C(12)-C(13)
1.381(5)
C(3)-O(3)
1.149(3)
C(12)-H(12)
0.9300
C(3)-Re(1)
1.921(3)
C(13)-C(14)
1.379(6)
C(4)-N(1)
1.339(4)
C(13)-H(13)
0.9300
C(4)-C(5)
1.381(4)
C(14)-C(15)
1.348(5)
C(4)-H(4)
0.9300
C(14)-H(14)
0.9300
C(5)-N(4)
1.332(4)
C(15)-C(16)
1.388(5)
C(5)-H(5)
0.9300
C(15)-H(15)
0.9300
C(6)-N(4)
1.336(4)
C(16)-N(3)
1.336(4)
C(6)-C(7)
1.380(4)
C(16)-H(16)
0.9300
C(6)-H(6)
0.9300
F(1)-P(1)
1.584(2)
C(7)-N(1)
1.358(3)
F(2)-P(1)
1.589(2)
C(7)-C(8)
1.465(4)
F(3)-P(1)
1.600(2)
C(8)-N(2)
1.350(3)
F(4)-P(1)
1.603(2)
C(8)-C(9)
1.389(4)
F(5)-P(1)
1.583(2)
C(9)-N(5)
1.333(4)
F(6)-P(1)
1.586(2)
C(9)-H(9)
0.9300
N(1)-Re(1)
2.161(2)
C(10)-N(5)
1.335(4)
N(2)-Re(1)
2.162(2)
C(10)-C(11)
1.385(4)
N(3)-Re(1)
2.202(2)
C(10)-H(10)
0.9300
_________________________________________________________________________
212
APPENDIX A (continued)
Bond angles [deg]
_________________________________________________________________________
O(1)-C(1)-Re(1)
178.9(3)
C(4)-N(1)-C(7)
117.2(2)
O(2)-C(2)-Re(1)
176.9(3)
C(4)-N(1)-Re(1)
126.33(19)
O(3)-C(3)-Re(1)
177.8(2)
C(7)-N(1)-Re(1)
116.37(18)
N(1)-C(4)-C(5)
121.1(3)
C(11)-N(2)-C(8)
117.4(2)
N(1)-C(4)-H(4)
119.5
C(11)-N(2)-Re(1)
125.56(18)
C(5)-C(4)-H(4)
119.5
C(8)-N(2)-Re(1)
117.02(17)
N(4)-C(5)-C(4)
122.7(3)
C(16)-N(3)-C(12)
116.8(3)
N(4)-C(5)-H(5)
118.6
C(16)-N(3)-Re(1)
121.3(2)
C(4)-C(5)-H(5)
118.6
C(12)-N(3)-Re(1)
121.8(2)
N(4)-C(6)-C(7)
123.3(3)
C(5)-N(4)-C(6)
115.7(3)
N(4)-C(6)-H(6)
118.4
C(9)-N(5)-C(10)
116.2(2)
C(7)-C(6)-H(6)
118.4
F(5)-P(1)-F(1)
90.25(14)
N(1)-C(7)-C(6)
120.0(3)
F(5)-P(1)-F(6)
90.83(13)
N(1)-C(7)-C(8)
115.7(2)
F(1)-P(1)-F(6)
91.34(14)
C(6)-C(7)-C(8)
124.3(2)
F(5)-P(1)-F(2)
179.23(14)
N(2)-C(8)-C(9)
120.3(2)
F(1)-P(1)-F(2)
90.50(12)
N(2)-C(8)-C(7)
115.3(2)
F(6)-P(1)-F(2)
88.99(12)
C(9)-C(8)-C(7)
124.4(2)
F(5)-P(1)-F(3)
90.06(14)
N(5)-C(9)-C(8)
122.7(3)
F(1)-P(1)-F(3)
88.99(13)
N(5)-C(9)-H(9)
118.6
F(6)-P(1)-F(3)
179.04(13)
C(8)-C(9)-H(9)
118.6
F(2)-P(1)-F(3)
90.11(12)
N(5)-C(10)-C(11)
122.5(3)
F(5)-P(1)-F(4)
90.08(14)
N(5)-C(10)-H(10)
118.8
F(1)-P(1)-F(4)
179.10(15)
C(11)-C(10)-H(10)
118.8
F(6)-P(1)-F(4)
89.49(14)
N(2)-C(11)-C(10)
120.9(3)
F(2)-P(1)-F(4)
89.17(13)
N(2)-C(11)-H(11)
119.6
F(3)-P(1)-F(4)
90.17(13)
C(10)-C(11)-H(11)
119.6
C(3)-Re(1)-C(2)
88.72(12)
N(3)-C(12)-C(13)
122.9(3)
C(3)-Re(1)-C(1)
89.13(11)
N(3)-C(12)-H(12)
118.6
C(2)-Re(1)-C(1)
90.02(12)
C(13)-C(12)-H(12)
118.6
C(3)-Re(1)-N(1)
94.55(10)
C(14)-C(13)-C(12)
118.7(4)
C(2)-Re(1)-N(1)
170.98(10)
C(14)-C(13)-H(13)
120.6
C(1)-Re(1)-N(1)
98.42(10)
C(12)-C(13)-H(13)
120.6
C(3)-Re(1)-N(2)
93.64(10)
C(15)-C(14)-C(13)
118.9(3)
C(2)-Re(1)-N(2)
96.39(10)
C(15)-C(14)-H(14)
120.6
C(1)-Re(1)-N(2)
173.07(10)
C(13)-C(14)-H(14)
120.6
N(1)-Re(1)-N(2)
75.04(8)
C(14)-C(15)-C(16)
120.2(3)
C(3)-Re(1)-N(3)
178.34(9)
C(14)-C(15)-H(15)
119.9
C(2)-Re(1)-N(3)
92.50(11)
C(16)-C(15)-H(15)
119.9
C(1)-Re(1)-N(3)
91.99(10)
N(3)-C(16)-C(15)
122.4(3)
N(1)-Re(1)-N(3)
84.07(8)
N(3)-C(16)-H(16)
118.8
N(2)-Re(1)-N(3)
85.11(8)
C(15)-C(16)-H(16)
118.8
213
APPENDIX A (continued)
Re(CO)3(Me2bpz)Cl
Atomic coordinates (x 104) and equivalent isotropic displacement parameters(Ǻ2 x 103)
U(eq) is defined as one third of the trace of the orthogonalized Uij tensor.
__________________________________________________________
x
y
z
U(eq)
__________________________________________________________
C(1)
1387(2)
716(2)
7479(3)
24(1)
C(2)
2302(2)
835(2)
6338(3)
20(1)
C(3)
1548(2)
1063(2)
5176(4)
21(1)
C(4)
1272(2)
1870(2)
7500(3)
22(1)
C(5)
1157(2)
2306(2)
7708(3)
22(1)
C(6)
2015(2)
2931(2)
6892(3)
26(1)
C(7)
2131(2)
2501(2)
6643(3)
19(1)
C(8)
2628(2)
2577(2)
5964(3)
18(1)
C(9)
3036(2)
3091(2)
5477(3)
21(1)
C(10)
3471(2)
2665(2)
4544(3)
20(1)
C(11)
3081(2)
2149(2)
5068(3)
19(1)
C(12)
610(2)
2192(2)
8268(4)
31(1)
C(13)
3914(2)
2696(2)
3706(3)
26(1)
Cl(1)
2577(1)
1750(1)
8406(1)
26(1)
N(1)
1753(1)
1961(1)
6957(2)
17(1)
N(2)
2658(1)
2101(1)
5765(2)
16(1)
N(3)
1530(1)
2841(1)
7386(3)
25(1)
N(4)
3453(1)
3142(1)
4767(3)
21(1)
O(1)
2488(1)
539(1)
6196(2)
29(1)
O(2)
1270(1)
899(1)
4347(2)
32(1)
O(3)
1022(1)
357(1)
8013(3)
37(1)
Re(1)
1996(1)
1328(1)
6608(1)
16(1)
_________________________________________________________
214
APPENDIX A (continued)
Anisotropic displacement parameters (Ǻ2 x 103)
The anisotropic displacement factor exponent takes the form:
-2 π2 [ h2 a*2 U11 + ... + 2 h k a* b* U12 ]
___________________________________________________________________
U11
U22
U33
U23
U13
U12
___________________________________________________________________
C(1)
30(2)
24(2)
24(2)
-6(2)
3(2)
17(2)
C(2)
26(2)
16(2)
17(2)
2(2)
3(2)
9(2)
C(3)
14(2)
17(2)
33(2)
-7(2)
3(2)
8(2)
C(4)
24(2)
24(2)
17(2)
-3(2)
-4(2)
12(2)
C(5)
28(2)
30(2)
14(2)
-6(2)
-7(2)
20(2)
C(6)
34(2)
22(2)
22(2)
1(2)
2(2)
15(2)
C(7)
27(2)
21(2)
12(2)
-2(2)
-6(2)
14(2)
C(8)
23(2)
20(2)
14(2)
-2(2)
-7(2)
12(2)
C(9)
26(2)
19(2)
21(2)
-2(2)
-6(2)
13(2)
C(10)
19(2)
23(2)
17(2)
0(2)
-5(2)
9(2)
C(11)
23(2)
19(2)
20(2)
-1(2)
0(2)
13(2)
C(12)
32(2)
34(2)
35(3)
-12(2)
-1(2)
23(2)
C(13)
27(2)
22(2)
27(2)
6(2)
5(2)
10(2)
Cl(1)
33(1)
25(1)
23(1)
-3(1)
-6(1)
16(1)
N(1)
23(2)
18(2)
13(2)
-3(1)
-4(1)
11(1)
N(2)
20(2)
15(2)
14(2)
0(1)
-4(1)
9(1)
N(3)
37(2)
26(2)
20(2)
-2(1)
1(2)
22(2)
N(4)
21(2)
23(2)
19(2)
0(1)
-5(1)
10(1)
O(1)
40(2)
28(2)
28(2)
0(1)
3(1)
23(1)
O(2)
35(2)
38(2)
30(2)
-8(1)
-5(1)
23(2)
O(3)
39(2)
25(2)
44(2)
8(1)
18(2)
14(1)
Re(1)
19(1)
14(1)
17(1)
-1(1)
0(1)
9(1)
_____________________________________________________________________________
215
APPENDIX A (continued)
Bond lengths [Ǻ]
___________________________________________________________________________
C(1)-O(3)
1.149(4)
C(8)-C(9)
1.386(5)
C(1)-Re(1)
1.923(4)
C(9)-N(4)
1.332(5)
C(2)-O(1)
1.151(4)
C(9)-H(9)
0.9300
C(2)-Re(1)
1.917(4)
C(10)-N(4)
1.342(4)
C(3)-O(2)
1.137(4)
C(10)-C(11)
1.392(5)
C(3)-Re(1)
1.925(4)
C(10)-C(13)
1.494(5)
C(4)-N(1)
1.343(4)
C(11)-N(2)
1.338(4)
C(4)-C(5)
1.387(5)
C(11)-H(11)
0.9300
C(4)-H(4)
0.9300
C(12)-H(12A)
0.9600
C(5)-N(3)
1.338(5)
C(12)-H(12B)
0.9600
C(5)-C(12)
1.493(5)
C(12)-H(12C)
0.9600
C(6)-N(3)
1.334(5)
C(13)-H(13A)
0.9600
C(6)-C(7)
1.379(5)
C(13)-H(13B)
0.9600
C(6)-H(6)
0.9300
C(13)-H(13C)
0.9600
C(7)-N(1)
1.349(4)
Cl(1)-Re(1)
2.4602(9)
C(7)-C(8)
1.470(5)
N(1)-Re(1)
2.158(3)
C(8)-N(2)
1.351(4)
N(2)-Re(1)
2.177(3)
216
APPENDIX A (continued)
Bond angles [deg]
________________________________________________________________________________
O(3)-C(1)-Re(1)
178.8(3)
H(12A)-C(12)-H(12C) 109.5
O(1)-C(2)-Re(1)
178.8(3)
H(12B)-C(12)-H(12C) 109.5
O(2)-C(3)-Re(1)
178.2(4)
C(10)-C(13)-H(13A)
109.5
N(1)-C(4)-C(5)
122.0(3)
C(10)-C(13)-H(13B)
109.5
N(1)-C(4)-H(4)
119.0
H(13A)-C(13)-H(13B) 109.5
C(5)-C(4)-H(4)
119.0
C(10)-C(13)-H(13C)
109.5
N(3)-C(5)-C(4)
120.6(3)
H(13A)-C(13)-H(13C) 109.5
N(3)-C(5)-C(12)
118.1(3)
H(13B)-C(13)-H(13C) 109.5
C(4)-C(5)-C(12)
121.2(3)
C(4)-N(1)-C(7)
117.3(3)
N(3)-C(6)-C(7)
123.4(4)
C(4)-N(1)-Re(1)
126.1(2)
N(3)-C(6)-H(6)
118.3
C(7)-N(1)-Re(1)
116.5(2)
C(7)-C(6)-H(6)
118.3
C(11)-N(2)-C(8)
117.4(3)
N(1)-C(7)-C(6)
119.6(3)
C(11)-N(2)-Re(1)
127.0(2)
N(1)-C(7)-C(8)
115.7(3)
C(8)-N(2)-Re(1)
115.7(2)
C(6)-C(7)-C(8)
124.5(3)
C(6)-N(3)-C(5)
116.8(3)
N(2)-C(8)-C(9)
119.7(3)
C(9)-N(4)-C(10)
116.6(3)
N(2)-C(8)-C(7)
116.1(3)
C(2)-Re(1)-C(1)
87.86(15)
C(9)-C(8)-C(7)
124.1(3)
C(2)-Re(1)-C(3)
91.12(15)
N(4)-C(9)-C(8)
123.4(3)
C(1)-Re(1)-C(3)
89.58(15)
N(4)-C(9)-H(9)
118.3
C(2)-Re(1)-N(1)
173.32(13)
C(8)-C(9)-H(9)
118.3
C(1)-Re(1)-N(1)
96.98(13)
N(4)-C(10)-C(11)
120.9(3)
C(3)-Re(1)-N(1)
93.50(12)
N(4)-C(10)-C(13)
118.6(3)
C(2)-Re(1)-N(2)
99.59(13)
C(11)-C(10)-C(13)
120.6(3)
C(1)-Re(1)-N(2)
171.92(13)
N(2)-C(11)-C(10)
121.9(3)
C(3)-Re(1)-N(2)
93.37(13)
N(2)-C(11)-H(11)
119.0
N(1)-Re(1)-N(2)
75.34(10)
C(10)-C(11)-H(11)
119.0
C(2)-Re(1)-Cl(1)
93.13(11)
C(5)-C(12)-H(12A)
109.5
C(1)-Re(1)-Cl(1)
93.33(11)
C(5)-C(12)-H(12B)
109.5
C(3)-Re(1)-Cl(1)
174.94(11)
H(12A)-C(12)-H(12B) 109.5
N(1)-Re(1)-Cl(1)
82.04(8)
C(5)-C(12)-H(12C)
109.5
N(2)-Re(1)-Cl(1)
83.22(7)
217
APPENDIX A (continued)
[Re(CO)3(Me2bpz)(py)]PF6
Atomic coordinates (x 104) and equivalent isotropic displacement parameters(Ǻ2 x 103)
U(eq) is defined as one third of the trace of the orthogonalized Uij tensor.
_________________________________________________________
x
y
z
U(eq)
_________________________________________________________
C(1)
9600(1)
1114(1)
1137(4)
30(1)
C(2)
9811(1)
1102(1)
3599(4)
30(1)
C(3)
9014(1)
420(1)
2680(4)
27(1)
C(4)
8601(1)
1145(1)
838(3)
22(1)
C(5)
8204(1)
1161(1)
485(4)
22(1)
C(6)
7978(1)
1063(1)
2532(4)
24(1)
C(7)
8370(1)
1045(1)
2901(3)
20(1)
C(8)
8482(1)
988(1)
4197(3)
22(1)
C(9)
8189(1)
890(1)
5222(4)
28(1)
C(10)
8720(1)
878(1)
6538(4)
24(1)
C(11)
9023(1)
988(1)
5549(4)
25(1)
C(12)
8109(1)
1214(1)
-851(4)
28(1)
C(13)
8859(1)
808(1)
7825(4)
30(1)
C(14)
9711(1)
2103(1)
1695(4)
25(1)
C(15)
9884(1)
2576(1)
1676(4)
30(1)
C(16)
9951(1)
2814(1)
2786(4)
29(1)
C(17)
9836(1)
2560(1)
3888(4)
29(1)
C(18)
9668(1)
2087(1)
3845(4)
26(1)
C(101)
10000
10000
3890(50)
93(14)
C(102)
10000
10000
5000
83(16)
C(103)
10000
10000
1172(18)
118(17)
C(104)
10000
10000
0
61(12)
F(1)
2285(1)
-88(1)
8753(2)
39(1)
F(2)
2595(1)
687(1)
8698(2)
45(1)
F(3)
3060(1)
384(1)
8537(2)
44(1)
F(4)
2636(1)
-61(1)
6908(2)
44(1)
F(5)
2938(1)
714(1)
6844(2)
48(1)
F(6)
2166(1)
246(1)
7057(3)
54(1)
N(1)
8687(1)
1091(1)
2027(3)
21(1)
N(2)
8905(1)
1035(1)
4374(3)
21(1)
N(3)
9600(1)
1853(1)
2763(3)
22(1)
N(4)
7894(1)
1125(1)
1348(3)
24(1)
N(5)
8300(1)
829(1)
6379(3)
29(1)
N(101)
10000
10000
3060(40)
72(8)
N(102)
10000
10000
2090(20)
84(9)
O(1)
9777(1)
1123(1)
207(3)
49(1)
218
APPENDIX A (continued)
O(2)
O(3)
P(1)
Re(1)
10099(1)
1101(1)
4195(3)
47(1)
8856(1)
25(1)
2687(3)
42(1)
2609(1)
310(1)
7791(1)
25(1)
9303(1)
1089(1)
2713(1)
21(1)
__________________________________________________________________________
Anisotropic displacement parameters (Ǻ2 x 103)
The anisotropic displacement factor exponent takes the form:
-2 π2 [ h2 a*2 U11 + ... + 2 h k a* b* U12 ]
___________________________________________________________________
U11
U22
U33
U23
U13
___________________________________________________________________
C(1)
29(2)
34(2)
27(2)
-6(2)
-6(2)
C(2)
27(2)
33(2)
26(2)
1(2)
5(2)
C(3)
23(2)
31(2)
28(2)
-3(2)
1(2)
C(4)
23(2)
23(2)
17(2)
-1(2)
2(2)
C(5)
20(2)
18(2)
26(2)
-3(2)
-4(2)
C(6)
22(2)
19(2)
29(2)
-2(2)
1(2)
C(7)
19(2)
14(2)
22(2)
-3(2)
3(2)
C(8)
23(2)
19(2)
23(2)
0(2)
2(2)
C(9)
25(2)
31(2)
26(2)
1(2)
5(2)
C(10)
29(2)
14(2)
24(2)
-1(2)
2(2)
C(11)
25(2)
22(2)
24(2)
-1(2)
0(2)
C(12)
28(2)
30(2)
28(2)
-1(2)
-1(2)
C(13)
33(2)
30(2)
23(2)
-2(2)
2(2)
C(14)
20(2)
32(2)
19(2)
-1(2)
-1(2)
C(15)
27(2)
30(2)
27(2)
7(2)
3(2)
C(16)
23(2)
23(2)
35(2)
1(2)
1(2)
C(17)
28(2)
29(2)
26(2)
-6(2)
0(2)
C(18)
21(2)
31(2)
21(2)
1(2)
2(2)
F(1)
45(2)
30(1)
30(1)
1(1)
10(1)
F(2)
67(2)
35(1)
41(2)
-9(1)
-1(1)
F(3)
33(1)
52(2)
47(2)
0(1)
-10(1)
F(4)
58(2)
33(1)
36(2)
-7(1)
12(1)
F(5)
58(2)
32(1)
36(2)
10(1)
6(1)
F(6)
41(2)
80(2)
44(2)
-3(2)
-16(1)
N(1)
19(2)
21(2)
19(2)
-3(1)
-1(1)
N(2)
21(2)
20(2)
19(2)
1(1)
-1(1)
N(3)
17(2)
23(2)
23(2)
-1(1)
1(1)
N(4)
22(2)
22(2)
27(2)
-2(1)
0(1)
N(5)
29(2)
31(2)
22(2)
2(1)
4(2)
O(1)
56(2)
74(2)
28(2)
1(2)
13(2)
O(2)
29(2)
66(2)
46(2)
10(2)
-9(2)
219
U12
17(2)
11(2)
14(2)
10(2)
7(2)
9(2)
4(2)
9(2)
12(2)
6(2)
9(2)
15(2)
13(2)
9(2)
11(2)
8(2)
12(2)
8(2)
9(1)
31(1)
21(1)
19(1)
10(1)
32(2)
8(1)
8(1)
8(1)
10(1)
11(2)
40(2)
22(2)
APPENDIX A (continued)
O(3)
P(1)
Re(1)
47(2)
28(1)
19(1)
31(2)
24(1)
25(1)
44(2)
22(1)
18(1)
-3(1)
-2(1)
-1(1)
-1(2)
-1(1)
0(1)
17(2)
11(1)
10(1)
Bond lengths [Ǻ]
__________________________________________________________________________
C(1)-O(1)
1.145(5)
C(13)-H(13B)
0.9600
C(1)-Re(1)
1.928(4)
C(13)-H(13C)
0.9600
C(2)-O(2)
1.149(5)
C(14)-N(3)
1.347(5)
C(2)-Re(1)
1.917(4)
C(14)-C(15)
1.379(5)
C(3)-O(3)
1.144(5)
C(14)-H(14)
0.9300
C(3)-Re(1)
1.930(4)
C(15)-C(16)
1.378(6)
C(4)-N(1)
1.331(5)
C(15)-H(15)
0.9300
C(4)-C(5)
1.396(5)
C(16)-C(17)
1.383(6)
C(4)-H(4)
0.9300
C(16)-H(16)
0.9300
C(5)-N(4)
1.341(5)
C(17)-C(18)
1.377(5)
C(5)-C(12)
1.487(5)
C(17)-H(17)
0.9300
C(6)-N(4)
1.331(5)
C(18)-N(3)
1.347(5)
C(6)-C(7)
1.389(5)
C(18)-H(18)
0.9300
C(6)-H(6)
0.9300
C(101)-N(101)
0.89(5)
C(7)-N(1)
1.355(4)
C(101)-C(102)
1.19(5)
C(7)-C(8)
1.467(5)
C(101)-N(102)
1.91(5)
C(8)-N(2)
1.350(5)
C(102)-C(101)#1
1.19(5)
C(8)-C(9)
1.387(5)
C(103)-N(102)
0.979(19)
C(9)-N(5)
1.332(5)
C(103)-C(104)
1.249(19)
C(9)-H(9)
0.9300
C(104)-C(103)#2
1.249(19)
C(10)-N(5)
1.331(5)
F(1)-P(1)
1.592(2)
C(10)-C(11)
1.375(5)
F(2)-P(1)
1.602(2)
C(10)-C(13)
1.502(5)
F(3)-P(1)
1.601(2)
C(11)-N(2)
1.344(5)
F(4)-P(1)
1.590(2)
C(11)-H(11)
0.9300
F(5)-P(1)
1.595(3)
C(12)-H(12A)
0.9600
F(6)-P(1)
1.585(3)
C(12)-H(12B)
0.9600
N(1)-Re(1)
2.176(3)
C(12)-H(12C)
0.9600
N(2)-Re(1)
2.160(3)
C(13)-H(13A)
0.9600
N(3)-Re(1)
2.216(3)
__________________________________________________________________________
220
APPENDIX A (continued)
Bond angles [deg]
________________________________________________________________________________
O(1)-C(1)-Re(1)
178.9(4)
C(15)-C(14)-H(14)
118.5
O(2)-C(2)-Re(1)
175.7(4)
C(16)-C(15)-C(14)
119.8(4)
O(3)-C(3)-Re(1)
177.4(4)
C(16)-C(15)-H(15)
120.1
N(1)-C(4)-C(5)
122.1(3)
C(14)-C(15)-H(15)
120.1
N(1)-C(4)-H(4)
118.9
C(15)-C(16)-C(17)
117.6(4)
C(5)-C(4)-H(4)
118.9
C(15)-C(16)-H(16)
121.2
N(4)-C(5)-C(4)
120.6(3)
C(17)-C(16)-H(16)
121.2
N(4)-C(5)-C(12)
117.9(3)
C(18)-C(17)-C(16)
119.9(4)
C(4)-C(5)-C(12)
121.5(3)
C(18)-C(17)-H(17)
120.1
N(4)-C(6)-C(7)
123.3(3)
C(16)-C(17)-H(17)
120.1
N(4)-C(6)-H(6)
118.4
N(3)-C(18)-C(17)
122.9(4)
C(7)-C(6)-H(6)
118.4
N(3)-C(18)-H(18)
118.6
N(1)-C(7)-C(6)
119.5(3)
C(17)-C(18)-H(18)
118.6
N(1)-C(7)-C(8)
115.4(3)
N(101)-C(101)-C(102) 180.00(3)
C(6)-C(7)-C(8)
125.1(3)
N(101)-C(101)-N(102)
0.00(3)
N(2)-C(8)-C(9)
119.0(3)
C(102)-C(101)-N(102) 180.00(3)
N(2)-C(8)-C(7)
115.7(3)
C(101)#1-C(102)-C(101) 180.00(3)
C(9)-C(8)-C(7)
125.3(3)
N(102)-C(103)-C(104) 180.000(18)
N(5)-C(9)-C(8)
123.3(4)
C(103)-C(104)-C(103)#2 180.000(10)
N(5)-C(9)-H(9)
118.3
C(4)-N(1)-C(7)
117.5(3)
C(8)-C(9)-H(9)
118.3
C(4)-N(1)-Re(1)
125.9(2)
N(5)-C(10)-C(11)
121.2(4)
C(7)-N(1)-Re(1)
116.6(2)
N(5)-C(10)-C(13)
118.7(3)
C(11)-N(2)-C(8)
117.6(3)
C(11)-C(10)-C(13)
120.1(4)
C(11)-N(2)-Re(1)
124.8(2)
N(2)-C(11)-C(10)
121.9(4)
C(8)-N(2)-Re(1)
117.0(2)
N(2)-C(11)-H(11)
119.1
C(14)-N(3)-C(18)
116.8(3)
C(10)-C(11)-H(11)
119.1
C(14)-N(3)-Re(1)
120.9(3)
C(5)-C(12)-H(12A)
109.5
C(18)-N(3)-Re(1)
122.2(3)
C(5)-C(12)-H(12B)
109.5
C(6)-N(4)-C(5)
116.9(3)
H(12A)-C(12)-H(12B) 109.5
C(10)-N(5)-C(9)
116.9(3)
C(5)-C(12)-H(12C)
109.5
C(103)-N(102)-C(101) 180.00(6)
H(12A)-C(12)-H(12C) 109.5
F(6)-P(1)-F(4)
90.74(15)
H(12B)-C(12)-H(12C) 109.5
F(6)-P(1)-F(1)
90.55(15)
C(10)-C(13)-H(13A)
109.5
F(4)-P(1)-F(1)
90.76(13)
C(10)-C(13)-H(13B)
109.5
F(6)-P(1)-F(5)
89.89(15)
H(13A)-C(13)-H(13B) 109.5
F(4)-P(1)-F(5)
89.89(14)
C(10)-C(13)-H(13C)
109.5
F(1)-P(1)-F(5)
179.21(17)
H(13A)-C(13)-H(13C) 109.5
F(6)-P(1)-F(3)
178.96(16)
H(13B)-C(13)-H(13C) 109.5
F(4)-P(1)-F(3)
90.12(15)
N(3)-C(14)-C(15)
123.0(4)
F(1)-P(1)-F(3)
90.02(14)
N(3)-C(14)-H(14)
118.5
F(5)-P(1)-F(3)
89.54(14)
221
APPENDIX A (continued)
F(6)-P(1)-F(2)
F(4)-P(1)-F(2)
F(1)-P(1)-F(2)
F(5)-P(1)-F(2)
F(3)-P(1)-F(2)
C(2)-Re(1)-C(1)
C(2)-Re(1)-C(3)
C(1)-Re(1)-C(3)
C(2)-Re(1)-N(2)
C(1)-Re(1)-N(2)
90.75(15)
178.50(16)
89.40(14)
89.94(14)
88.39(14)
90.10(17)
87.74(17)
89.04(17)
95.38(14)
174.22(14)
C(3)-Re(1)-N(2)
C(2)-Re(1)-N(1)
C(1)-Re(1)-N(1)
C(3)-Re(1)-N(1)
N(2)-Re(1)-N(1)
C(2)-Re(1)-N(3)
C(1)-Re(1)-N(3)
C(3)-Re(1)-N(3)
N(2)-Re(1)-N(3)
N(1)-Re(1)-N(3)
222
89.34(14)
170.04(14)
99.72(14)
94.06(14)
74.86(11)
94.53(14)
92.58(14)
177.21(13)
88.83(11)
83.42(11)
APPENDIX B
CHAPTER 3 SUPPLEMENTARY INFORMATION
[Ru(bpy)(Obpy)]2+
Cartesian Coordinates from calculations
Atom
Re
N
C
C
C
C
C
H
H
H
N
C
C
C
H
C
C
H
H
H
N
C
C
C
C
H
C
H
H
H
N
C
C
C
C
X
-0.013778
-0.072699
1.153888
-1.180205
1.254941
-1.135899
0.084109
2.219806
-2.035004
0.131132
0.404744
1.622494
-0.703243
1.789470
2.477420
-0.595715
0.656797
2.782854
-1.475955
0.747948
-1.877266
-1.958615
-2.959219
-3.149843
-4.159989
-2.849703
-4.266365
-3.204119
-4.988031
-5.187148
-0.697037
-0.410966
-1.402051
-0.713873
-1.738507
Coordinates
Y
0.063187
0.020134
-0.206737
0.127362
-0.591278
-0.264224
-0.684874
-0.797839
-0.206519
-1.010526
-2.006188
-2.589106
-2.825019
-3.971723
-1.928944
-4.219781
-4.804544
-4.378584
-4.847578
-5.878741
-0.771837
-2.144197
-0.090204
-2.828100
-0.719244
0.981809
-2.115194
-3.906052
-0.127801
-2.633834
2.045735
2.555360
2.831092
3.879057
4.161278
223
Z
-0.001508
2.105339
2.690007
2.895992
4.038474
4.246138
4.808600
4.486506
4.850614
5.842936
0.068220
0.270643
-0.038399
0.415380
0.306244
0.120359
0.359133
0.570744
0.053384
0.483536
-0.507964
-0.405108
-0.987681
-0.719537
-1.332395
-1.082423
-1.178620
-0.627333
-1.707946
-1.425234
-0.247771
-1.511025
0.636491
-1.863775
0.293282
APPENDIX B (continued)
C
H
H
H
N
C
C
C
C
H
C
H
H
H
N
C
C
C
C
H
C
H
H
H
C
C
H
H
H
H
-1.370016
-0.459660
-2.285701
-1.610467
1.954769
2.297495
2.931178
3.629325
4.269121
2.626386
4.629888
3.881013
5.006392
5.659910
0.349610
0.165743
0.811602
0.479351
1.129214
0.927506
0.967706
0.341138
1.493498
1.210724
-2.325414
-1.835503
-1.015782
-2.649874
-2.739799
-3.132227
4.705411
4.262483
4.763881
5.733846
0.529485
0.148410
1.013086
0.216204
1.116146
1.315133
0.699428
-0.084880
1.512817
0.761005
0.317068
1.602929
-0.639013
1.937214
-0.361946
-1.634662
0.953211
2.948073
-1.155522
1.204493
0.921488
2.384731
2.615004
3.058719
0.465301
0.970425
-0.941852
-2.843718
1.010494
-1.190545
0.544477
1.828740
-0.275791
2.278182
0.124211
-1.268863
1.420440
3.288446
-0.565322
1.756667
-2.023740
-2.484703
-2.879254
-3.817760
-4.213479
-2.471145
-4.690626
-4.180863
-4.856778
-5.718056
2.314445
2.034850
2.731767
2.319518
1.416840
3.052568
TDDFT Singlet Excited States
Excited State 1: Singlet-A 2.4193 eV 512.47 nm f=0.0098
135 ->138
-0.11687
136 ->138
0.29885
136 ->139
-0.15070
137 ->138
0.44733
137 ->139
-0.36172
This state for optimization and/or second-order correction.
Total Energy, E(RPA) = -1657.86807045
Copying the excited state density for this state as the 1-particle RhoCI density.
224
APPENDIX B (continued)
Excited State 2: Singlet-A
136 ->138
0.24347
137 ->138
0.28964
137 ->139
0.56168
137 ->140
0.11921
2.4833 eV 499.28 nm f=0.0046
Excited State 3: Singlet-A
135 ->138
-0.12194
135 ->139
0.19803
136 ->138
0.34125
136 ->139
-0.31571
136 ->140
-0.34206
137 ->138
-0.22502
137 ->140
-0.17968
2.5426 eV 487.62 nm f=0.0161
Excited State 4: Singlet-A
135 ->138
0.29884
135 ->140
-0.20427
136 ->138
0.13478
136 ->139
-0.27550
136 ->140
0.23566
137 ->138
-0.20187
137 ->140
0.39319
2.5591 eV 484.49 nm f=0.0185
Excited State 5: Singlet-A
135 ->138
0.27867
135 ->139
-0.15366
136 ->138
0.40588
136 ->139
0.41543
136 ->140
-0.10703
137 ->138
-0.12024
137 ->139
-0.13869
2.5738 eV 481.71 nm f=0.0102
Excited State 6: Singlet-A
135 ->138
0.53553
135 ->139
0.11509
135 ->140
0.16373
136 ->138
-0.11621
136 ->139
-0.16787
136 ->140
-0.14714
137 ->138
0.23377
2.6425 eV 469.19 nm f=0.0398
225
APPENDIX B (continued)
137 ->140
-0.17563
Excited State 7: Singlet-A
135 ->139
0.11229
135 ->140
0.49080
136 ->138
0.10643
136 ->140
0.39992
137 ->138
-0.15739
137 ->139
0.10002
137 ->140
-0.12057
2.7352 eV 453.29 nm f=0.0314
Excited State 8: Singlet-A
135 ->139
0.49281
135 ->140
-0.30545
136 ->139
0.21610
136 ->140
0.19309
137 ->140
-0.20170
2.8009 eV 442.66 nm f=0.1046
Excited State 9: Singlet-A
135 ->139
0.33259
135 ->140
0.24014
136 ->139
0.14511
136 ->140
-0.22296
136 ->144
-0.11937
137 ->140
0.36408
137 ->144
-0.10417
137 ->145
-0.12400
2.9946 eV 414.03 nm f=0.0007
Excited State 10: Singlet-A
136 ->141
0.13499
137 ->141
0.67920
3.3515 eV 369.93 nm f=0.0111
Excited State 11: Singlet-A
136 ->141
0.67171
137 ->141
-0.13623
3.4529 eV 359.07 nm f=0.0065
Excited State 12: Singlet-A
135 ->142
-0.10908
136 ->144
-0.10346
137 ->142
0.46020
137 ->143
0.19560
137 ->144
0.21097
137 ->145
-0.21218
3.5078 eV 353.45 nm f=0.0046
226
APPENDIX B (continued)
137 ->146
137 ->151
-0.16689
0.17857
Excited State 13: Singlet-A
135 ->141
0.68625
3.5513 eV 349.12 nm f=0.0034
Excited State 14: Singlet-A
135 ->142
-0.17450
135 ->151
-0.10366
136 ->142
0.31516
136 ->145
-0.10963
136 ->150
-0.14006
136 ->151
0.13291
137 ->142
0.29736
137 ->143
-0.25123
137 ->144
-0.30977
137 ->150
-0.11768
3.5788 eV 346.44 nm f=0.0102
Excited State 15: Singlet-A
135 ->142
-0.12817
135 ->151
-0.10470
136 ->142
0.37651
136 ->145
-0.10868
136 ->151
0.16380
137 ->142
-0.22152
137 ->143
0.38310
137 ->144
0.10345
3.6060 eV 343.83 nm f=0.0061
Excited State 16: Singlet-A
135 ->142
0.17873
135 ->144
0.12502
135 ->151
0.11269
136 ->143
0.17652
136 ->145
0.14785
137 ->142
0.24228
137 ->143
0.36138
137 ->144
-0.32098
137 ->145
0.15395
137 ->146
0.15192
3.6363 eV 340.96 nm f=0.0089
Excited State 17: Singlet-A
134 ->138
0.10180
135 ->142
0.14273
3.6750 eV 337.37 nm f=0.0091
227
APPENDIX B (continued)
135 ->143
135 ->144
136 ->142
136 ->145
137 ->142
137 ->143
137 ->144
137 ->145
137 ->146
0.16774
0.13104
0.27594
0.12717
0.16479
-0.18511
0.39341
0.19076
0.14963
Excited State 18: Singlet-A
132 ->138
0.10390
136 ->143
0.41030
136 ->144
0.28468
136 ->145
0.12012
136 ->146
-0.12595
136 ->150
0.11382
137 ->143
-0.19755
137 ->145
-0.29060
137 ->146
-0.12296
137 ->150
0.10831
3.6875 eV 336.23 nm f=0.0286
Excited State 19: Singlet-A
136 ->143
-0.38030
136 ->144
0.39254
136 ->145
-0.12445
137 ->145
-0.24440
137 ->146
0.25860
3.7183 eV 333.45 nm f=0.0166
Excited State 20: Singlet-A
135 ->142
0.36403
135 ->143
-0.12617
135 ->145
-0.21985
135 ->151
0.11376
136 ->142
0.26634
136 ->143
-0.16200
136 ->144
-0.15549
136 ->146
-0.10740
137 ->145
-0.15045
137 ->146
-0.29641
3.7236 eV 332.97 nm f=0.0061
Excited State 21: Singlet-A
135 ->143
-0.25468
3.7459 eV 330.98 nm f=0.0304
228
APPENDIX B (continued)
135 ->145
135 ->150
136 ->143
136 ->144
136 ->145
136 ->150
137 ->144
137 ->145
137 ->146
137 ->150
-0.11223
-0.14759
0.22711
-0.15209
-0.13653
-0.12158
0.15055
-0.21852
0.33311
-0.22205
Excited State 22: Singlet-A
135 ->142
-0.12527
135 ->143
-0.14234
135 ->144
-0.22216
135 ->146
0.15196
135 ->150
-0.12091
136 ->143
-0.11306
136 ->144
0.13318
136 ->145
0.51233
136 ->150
-0.12985
3.7724 eV 328.66 nm f=0.0015
Excited State 23: Singlet-A
136 ->144
0.30270
136 ->146
0.45877
136 ->150
-0.19023
137 ->146
-0.20293
137 ->150
-0.18071
3.7878 eV 327.32 nm f=0.0033
Excited State 24: Singlet-A
135 ->142
0.22295
135 ->143
0.33466
135 ->144
-0.30372
135 ->146
0.17794
136 ->142
-0.13575
136 ->146
-0.30993
136 ->150
-0.16175
3.8264 eV 324.03 nm f=0.0023
Excited State 25: Singlet-A
133 ->139
0.12891
135 ->142
0.12673
135 ->144
0.34081
135 ->145
0.39923
3.8468 eV 322.30 nm f=0.0192
229
APPENDIX B (continued)
135 ->146
136 ->145
136 ->146
136 ->150
137 ->150
-0.12802
0.18048
-0.15601
-0.16263
-0.13869
Excited State 26: Singlet-A
135 ->142
-0.23618
135 ->143
0.17888
135 ->144
0.35657
135 ->145
-0.34080
135 ->146
0.15141
136 ->146
-0.16637
136 ->150
-0.12252
137 ->146
-0.11357
137 ->150
-0.13650
3.8709 eV 320.30 nm f=0.0239
Excited State 27: Singlet-A
133 ->139
-0.15759
135 ->142
0.21321
135 ->143
-0.28400
135 ->144
0.16524
135 ->146
0.48916
137 ->145
0.12200
137 ->150
0.13451
3.8792 eV 319.61 nm f=0.0015
Excited State 28: Singlet-A
134 ->138
0.44879
134 ->140
0.10378
135 ->143
-0.14977
135 ->144
-0.12910
135 ->150
0.23309
136 ->142
-0.15498
136 ->151
0.24151
137 ->151
-0.14732
4.0099 eV 309.19 nm f=0.0344
Excited State 29: Singlet-A
133 ->138
-0.15206
134 ->138
0.37093
134 ->140
0.24080
135 ->143
0.10232
135 ->150
-0.20458
136 ->151
-0.17368
4.0662 eV 304.91 nm f=0.0146
230
APPENDIX B (continued)
137 ->146
0.12442
137 ->150
0.11288
137 ->151
0.20598
Excited State 30: Singlet-A
133 ->138
0.45647
135 ->142
0.10248
135 ->145
-0.17775
135 ->146
-0.17721
135 ->151
-0.22886
136 ->150
-0.19080
137 ->150
0.15389
137 ->151
0.15633
4.0814 eV 303.78 nm f=0.0064
Excited State 31: Singlet-A
133 ->138
0.50588
134 ->138
0.12700
134 ->140
0.11737
135 ->145
0.16319
135 ->146
0.17381
135 ->151
0.18646
136 ->150
0.16203
136 ->151
-0.13749
137 ->150
-0.10814
4.0856 eV 303.46 nm f=0.0082
Excited State 32: Singlet-A
134 ->138
0.11043
134 ->139
0.68506
4.1054 eV 302.00 nm f=0.0014
Excited State 33: Singlet-A
132 ->138
-0.11257
132 ->139
0.12351
133 ->139
0.14643
133 ->140
0.17852
134 ->140
-0.12893
135 ->143
-0.21568
135 ->146
-0.15982
135 ->150
-0.19463
136 ->144
0.15161
136 ->145
-0.16725
136 ->146
-0.16240
137 ->145
0.25506
4.2261 eV 293.38 nm f=0.0094
Excited State 34: Singlet-A
4.2583 eV 291.16 nm f=0.0732
231
APPENDIX B (continued)
132 ->138
132 ->140
134 ->138
134 ->140
136 ->146
0.41158
-0.17529
-0.12052
0.41151
-0.10417
Excited State 35: Singlet-A
132 ->138
-0.25739
132 ->139
-0.26656
132 ->140
0.13795
133 ->139
-0.30051
133 ->140
0.40564
134 ->140
0.17093
4.2873 eV 289.19 nm f=0.0473
Excited State 36: Singlet-A
132 ->138
-0.12468
132 ->139
0.60683
132 ->140
0.12106
133 ->140
0.10758
134 ->140
0.20752
4.3050 eV 288.00 nm f=0.0311
Excited State 37: Singlet-A
132 ->138
0.24247
132 ->140
-0.20111
133 ->139
0.14067
133 ->140
0.53250
134 ->140
-0.13601
4.3239 eV 286.74 nm f=0.0357
Excited State 38: Singlet-A
132 ->139
-0.17395
132 ->140
0.32259
133 ->139
0.40460
134 ->140
0.16168
135 ->145
-0.12228
4.4165 eV 280.73 nm f=0.3605
Excited State 39: Singlet-A
135 ->150
0.12037
135 ->151
-0.15526
136 ->150
0.25167
136 ->151
0.11937
137 ->147
-0.14744
137 ->150
-0.30899
137 ->151
0.37710
4.4432 eV 279.04 nm f=0.0117
232
APPENDIX B (continued)
Excited State 40: Singlet-A
132 ->138
0.25555
132 ->140
0.46185
132 ->141
-0.11322
133 ->139
-0.15422
134 ->140
-0.16411
4.5285 eV 273.79 nm f=0.4936
Excited State 41: Singlet-A
135 ->147
-0.15208
135 ->150
-0.33686
136 ->146
0.10643
136 ->148
0.14482
136 ->149
0.12465
136 ->150
0.12524
136 ->151
0.38152
136 ->152
-0.10698
137 ->151
-0.12116
4.5423 eV 272.95 nm f=0.0144
Excited State 42: Singlet-A
135 ->148
0.10361
135 ->151
0.43313
135 ->152
-0.10630
136 ->150
-0.14807
136 ->151
0.21452
137 ->148
0.12940
137 ->151
0.28385
4.6633 eV 265.87 nm f=0.0282
Excited State 43: Singlet-A
134 ->141
0.65238
134 ->144
0.10519
4.8462 eV 255.84 nm f=0.0067
Excited State 44: Singlet-A
133 ->141
0.59473
137 ->147
-0.21936
4.9033 eV 252.86 nm f=0.0150
Excited State 45: Singlet-A
131 ->138
0.15684
132 ->141
-0.18915
133 ->141
0.22150
134 ->142
-0.14850
137 ->147
0.49389
137 ->150
-0.15638
4.9420 eV 250.88 nm f=0.0085
233
APPENDIX B (continued)
Excited State 46: Singlet-A
131 ->138
-0.22644
134 ->142
0.42040
134 ->145
-0.12218
134 ->146
-0.15243
136 ->147
0.19941
136 ->149
0.11020
136 ->150
-0.10202
137 ->147
0.21212
137 ->148
-0.12159
4.9874 eV 248.59 nm f=0.0264
Excited State 47: Singlet-A
132 ->141
-0.31913
133 ->145
0.11069
134 ->142
0.14271
136 ->147
-0.20883
137 ->148
0.41462
137 ->149
-0.19707
5.0028 eV 247.83 nm f=0.0023
Excited State 48: Singlet-A
132 ->141
0.22835
134 ->141
-0.10342
134 ->143
-0.28649
136 ->147
0.31863
137 ->148
0.33379
137 ->149
0.17405
137 ->150
-0.14380
137 ->151
-0.10589
5.0315 eV 246.41 nm f=0.0126
Excited State 49: Singlet-A
130 ->138
-0.11208
134 ->143
0.17618
134 ->144
-0.16842
136 ->147
0.41988
136 ->148
-0.11989
136 ->149
-0.11566
137 ->149
-0.33715
5.0445 eV 245.78 nm f=0.0077
Excited State 50: Singlet-A
129 ->138
-0.13560
131 ->138
-0.26816
132 ->141
0.34837
133 ->142
-0.11241
5.0711 eV 244.49 nm f=0.0159
234
APPENDIX B (continued)
134 ->142
134 ->143
136 ->147
136 ->148
136 ->149
137 ->147
137 ->148
137 ->149
-0.10941
0.15626
-0.17977
0.16616
-0.10751
0.19300
0.12887
-0.19281
TDDFT Triplet Results
Excited State 1: ?Spin -A
138A ->139A
0.26048
124B ->137B
-0.12604
126B ->137B
0.10917
131B ->137B
-0.11442
132B ->137B
-0.14136
133B ->137B
0.17262
134B ->137B
0.20078
135B ->137B
-0.44609
136B ->137B
1.05012
136B ->140B
-0.12428
0.1327 eV 9343.73 nm f=0.0005
This state for optimization and/or second-order correction.
Total Energy, E(RPA) = -1657.87361623
Copying the excited state density for this state as the 1-particle RhoCI density.
Excited State 2: ?Spin -A
138A ->139A
0.54919
136B ->137B
-0.42165
0.1675 eV 7400.79 nm f=0.0051
Excited State 3: ?Spin -A
138A ->140A
0.57428
132B ->137B
0.10888
135B ->137B
0.50650
136B ->137B
0.13122
0.2294 eV 5405.33 nm f=0.0073
Excited State 4: ?Spin -A
138A ->140A
-0.28583
123B ->137B
0.12000
132B ->137B
0.19626
134B ->137B
0.20372
135B ->137B
0.80255
0.2678 eV 4629.10 nm f=0.0036
235
APPENDIX B (continued)
135B ->140B
-0.10006
136B ->137B
0.30066
Excited State 5: ?Spin -A
138A ->141A
1.00104
0.9335 eV 1328.11 nm f=0.0027
[(Ru(bpy)2)2Obpy]4+
Cartesian Coordinates from Calculation
Atom
Ru
N
C
C
C
C
H
C
H
H
H
N
C
C
C
C
H
C
H
H
H
N
C
C
C
C
C
H
H
H
N
X
0.000000
0.000000
1.245325
-1.109592
1.377519
-1.035683
-2.065956
0.230255
2.358947
-1.948054
0.320240
2.048980
2.385375
3.044944
3.725665
4.393001
2.736704
4.741027
3.972665
5.142178
5.771344
-0.837537
-0.230562
-2.203376
-0.972020
-2.962931
-2.342228
-0.481690
-4.022383
-2.911833
0.200311
Coordinates
Y
0.000000
0.000000
0.000000
0.030470
0.038061
0.072387
0.035053
0.079228
0.042539
0.108438
0.121995
-0.212937
-0.027925
-0.224919
0.166220
-0.035778
-0.366235
0.173588
0.346580
-0.025246
0.362199
-2.029462
-3.269568
-2.000103
-4.454751
-3.172798
-4.416811
-5.411019
-3.117854
-5.330755
0.164260
236
Z
0.000000
2.089145
2.687705
2.882421
4.088698
4.280656
2.375814
4.897695
4.548968
4.866300
5.978463
0.422894
1.750203
-0.509994
2.139605
-0.179258
-1.538580
1.170388
3.179443
-0.963917
1.455877
-0.050679
0.078052
-0.308162
-0.086528
-0.475626
-0.371946
0.010279
-0.685286
-0.504808
-2.084433
APPENDIX B (continued)
C
C
C
H
C
C
H
H
H
N
C
C
C
C
H
C
H
H
H
N
C
C
C
H
C
C
H
H
H
C
H
H
C
H
H
C
C
N
C
H
Ru
C
C
-0.007506
0.522054
0.094130
-0.265801
0.637845
0.421876
-0.087877
0.884185
0.501914
-2.028086
-2.855436
-2.570059
-4.240363
-3.937250
-1.890881
-4.791379
-4.895899
-4.316503
-5.856162
0.515522
0.662547
0.719249
1.011290
0.480264
1.074170
1.223734
1.108966
1.230396
1.493640
1.260798
1.804884
1.444348
1.820813
1.236841
1.694250
3.292181
4.073598
3.840017
5.418991
3.635895
3.030105
5.161504
5.961919
-0.835065
1.423536
-0.636348
-1.804190
1.679823
0.645205
-1.462150
2.672581
0.835496
0.408537
-0.675943
1.661181
-0.503050
1.889936
2.489147
0.786567
-1.354244
2.906064
0.925812
2.017185
2.909254
2.448732
4.249052
2.537031
3.783925
4.696447
4.921077
4.115963
5.728565
-3.349614
-2.843331
-2.761785
-4.792067
-5.320547
-5.361730
-4.865109
-3.693530
-6.084265
-3.725269
-2.755786
-8.128655
-6.098750
-4.941686
237
-2.988434
-2.550581
-4.371185
-2.581219
-3.929767
-4.853445
-5.050463
-4.287038
-5.918912
-0.228206
-0.391827
-0.255012
-0.595208
-0.447691
-0.114659
-0.627359
-0.725093
-0.458150
-0.784026
-0.211628
0.810294
-1.506761
0.597528
1.809885
-1.777179
-0.720588
1.443349
-2.796562
-0.920199
0.399357
-0.407920
1.306611
0.590461
1.354052
-0.338771
0.996930
1.003505
1.362965
1.389507
0.696748
1.252404
1.791848
1.801818
APPENDIX B (continued)
H
N
N
N
N
N
C
H
C
C
C
C
C
C
C
C
C
C
C
C
H
C
C
H
C
H
C
C
H
C
C
H
C
H
C
H
H
C
H
H
H
C
H
6.026111
3.654528
1.199668
4.904245
2.230738
2.474082
5.719048
6.996307
2.646006
4.948061
1.277491
-0.029232
5.359746
1.754596
2.198018
1.865497
2.650028
7.000400
2.936451
5.293791
5.710711
0.116234
-1.213997
-0.044913
6.625460
4.695768
1.229925
1.689726
2.601373
1.421877
2.233112
3.146236
7.463699
7.637816
4.270799
2.137397
6.337672
-1.142362
0.192126
-2.161711
6.939385
1.193518
1.693440
-2.826216
-8.213526
-7.963225
-8.484500
-8.197992
-10.136749
-7.390248
-4.990545
-8.191834
-8.289991
-8.146484
-7.977573
-9.709512
-9.430335
-7.160745
-10.504352
-11.077724
-7.522695
-8.239821
-8.346403
-8.320795
-8.338851
-8.180615
-7.842612
-9.899371
-10.548050
-9.618688
-7.292615
-6.219824
-11.824194
-12.406342
-10.752347
-8.783819
-6.660136
-8.319275
-8.220748
-8.417544
-8.365709
-8.506116
-8.219834
-10.895212
-8.543831
-6.440360
238
1.374599
-0.747641
0.227287
2.084086
3.185085
1.396448
2.247391
2.113926
-1.691163
-1.174369
-1.139704
0.820244
2.479185
3.587632
4.069212
2.580348
0.425036
2.821356
-3.067599
-2.530845
-0.407288
-1.914505
0.101200
1.894665
3.045491
2.329604
4.880310
5.367500
3.716116
2.785582
0.579530
-0.479914
3.224799
2.966713
-3.497889
-3.799690
-2.817075
-1.293959
-2.982558
0.628232
3.339174
5.782354
6.038469
APPENDIX B (continued)
C
H
H
H
H
H
H
H
H
1.602910
0.944462
2.401857
8.448608
4.506142
-2.038100
0.798488
1.267061
0.864562
-12.787527
-12.106071
-13.119999
-8.892342
-8.366227
-8.550320
-8.681663
-13.808525
-10.590496
1.779603
3.716585
-0.219679
3.667357
-4.556331
-1.878742
6.783780
1.930302
5.190403
TDDFT Triplet Results
Excited state symmetry could not be determined.
Excited State 1: ?Spin -?Sym 0.1014 eV 12225.55 nm f=0.0033
268A ->269A
-0.72652
268A ->270A
-0.12753
This state for optimization and/or second-order correction.
Total Energy, E(RPA) = -3238.24009815
Copying the excited state density for this state as the 1-particle RhoCI density.
Excited state symmetry could not be determined.
Excited State 2: ?Spin -?Sym 0.1225 eV 10124.90 nm f=0.0034
268A ->269A
0.20897
268A ->270A
-0.47798
Excited state symmetry could not be determined.
Excited State 3: ?Spin -?Sym 0.2835 eV 4373.23 nm f=0.0000
238B ->267B
0.19968
256B ->267B
0.10802
259B ->267B
-0.18012
260B ->267B
0.39735
262B ->267B
0.74383
263B ->267B
0.63812
Excited state symmetry could not be determined.
Excited State 4: ?Spin -?Sym 0.3336 eV 3716.06 nm f=0.0003
234B ->267B
0.12559
237B ->267B
-0.14027
258B ->267B
-0.59718
259B ->267B
-0.54307
261B ->267B
-0.32758
239
APPENDIX B (continued)
262B ->267B
263B ->267B
0.37613
-0.46467
Excited state symmetry could not be determined.
Excited State 5: ?Spin -?Sym 0.5149 eV 2407.76 nm f=0.0018
268A ->271A
0.99143
[Ru(bpy)3]2+
Cartesian Coordinates from calculations
Atom
Ru
N
C
C
C
C
H
C
H
H
H
N
C
C
C
C
H
C
H
H
H
N
C
C
C
H
C
C
H
X
-0.005579
-0.048855
1.173270
-1.169278
1.271028
-1.129138
-2.105609
0.113704
2.234047
-2.048869
0.179040
2.020744
2.329307
3.032141
3.661333
4.373457
2.746518
4.696279
3.894169
5.141066
5.726361
-0.494445
0.387287
-1.834300
-0.012508
1.427530
-2.291209
-1.377307
0.728188
Coordinates
Y
0.060399
-0.003083
-0.179353
0.087796
-0.263199
0.013140
0.226208
-0.166731
-0.405038
0.092242
-0.230734
-0.193225
-0.266898
-0.265445
-0.416420
-0.415844
-0.203822
-0.492013
-0.470779
-0.469289
-0.606245
-1.972821
-3.002304
-2.262128
-4.344213
-2.731232
-3.593586
-4.647571
-5.126904
240
Z
-0.059220
2.030848
2.648027
2.802966
4.049799
4.200695
2.277884
4.837871
4.525810
4.770143
5.919254
0.390672
1.734324
-0.521520
2.164598
-0.148898
-1.563841
1.219664
3.221424
-0.913323
1.541566
-0.091888
0.058973
-0.256757
0.048975
0.186006
-0.273521
-0.119613
0.172298
APPENDIX B (continued)
H
H
N
C
C
C
H
C
C
H
H
H
N
C
C
C
C
H
C
H
H
H
N
C
C
C
H
C
C
H
H
H
-3.344941
-1.719996
0.240019
0.161028
0.478850
0.317326
-0.026848
0.643173
0.562648
0.246142
0.828861
0.686550
-2.076920
-2.714184
-2.817391
-4.104487
-4.202585
-2.276682
-4.860129
-4.596515
-4.746645
-5.932333
0.328758
0.373194
0.545448
0.625703
0.198008
0.805425
0.846911
0.649366
0.976953
1.047401
-3.810925
-5.677246
0.275721
-0.731063
1.561653
-0.512876
-1.723531
1.837549
0.795698
-1.347962
2.850112
0.998768
0.135301
-1.087021
1.272861
-1.167089
1.251069
2.208095
0.008233
-2.130643
2.184321
-0.043619
2.118753
3.001626
2.586282
4.366910
2.594217
3.948937
4.851530
5.028272
4.306491
5.903695
-0.401730
-0.129842
-2.124357
-3.041056
-2.566415
-4.415281
-2.651988
-3.937121
-4.874043
-5.103740
-4.275192
-5.932887
-0.336368
-0.410573
-0.467753
-0.616151
-0.671485
-0.402373
-0.748421
-0.676145
-0.768675
-0.907912
-0.224999
0.813671
-1.505931
0.632006
1.801076
-1.745360
-0.671468
1.491348
-2.753725
-0.846130
TDDFT Triplet Results
Excited state symmetry could not be determined.
Excited State 1: ?Spin -?Sym 0.0889 eV 13946.41 nm f=0.0018
131A ->132A
0.42552
This state for optimization and/or second-order correction.
Total Energy, E(RPA) = -1580.48243672
Copying the excited state density for this state as the 1-particle RhoCI density.
241
APPENDIX B (continued)
Excited state symmetry could not be determined.
Excited State 2: ?Spin -?Sym 0.0935 eV 13260.08 nm f=0.0020
131A ->133A
0.43745
Excited state symmetry could not be determined.
Excited State 3: ?Spin -?Sym 0.2604 eV 4760.62 nm f=0.0001
116B ->130B
-0.18723
117B ->130B
0.12604
126B ->130B
0.11543
127B ->130B
0.35893
128B ->130B
0.76862
129B ->130B
-0.67532
Excited state symmetry could not be determined.
Excited State 4: ?Spin -?Sym 0.2606 eV 4757.14 nm f=0.0001
116B ->130B
0.12589
117B ->130B
0.18739
126B ->130B
0.35677
127B ->130B
-0.11642
128B ->130B
0.67614
129B ->130B
0.76831
Excited state symmetry could not be determined.
Excited State 5: ?Spin -?Sym 0.8508 eV 1457.26 nm f=0.0000
131A ->134A
1.01491
242
Detailed TDDFT Triplet State Results
Compound
O-Bpy
Bpy
f
1
2
0.001
0.005
3
0.007
4
0.004
1
0.003
2
3
0.003
0.000
4
0.000
1
0.002
2
3
0.002
0.000
4
0.000
Transition
H-2 → H-1 (0.7)
H → L (0.6)
H-2 → H-1 (0.4)
H → L+1 (0.5)
H-3 → H-1 (0.4)
H-3 → H-1 (0.7)
H → L (1.0)
H→L+1
(0.8)
H-6→H-1 (0.5)
H-5→H-1 (0.3)
H-9→H-1 (0.4)
H-8→H-1 (0.3)
H → L (1.0)
H→L+1
(1.0)
H-3→H-1 (0.5)
H-2→H-1 (0.4)
H-3→H-1 (0.4)
H-2→H-1 (0.5)
Type
Singlet Triplet Energy Gap
Ru(0.6)
→
Bpy(0.4),O-Bpy(0.6)
→
Ru(0.6)
→
Bpy(0.4),O-Bpy(0.6)
→
Ru(0.6)
→
Ru(0.6)
→
Singlet Triplet Energy Gap
Bpy(0.6),O-Bpy(0.4)
→
Bpy(0.6),O-Bpy(0.4)
Ru(0.4), L(0.6)
Ru(0.3), L(0.7)
Ru(0.3), L(0.7)
Ru(0.2), L(0.8)
→
→
→
→
→
Singlet Triplet Energy Gap
Bpy(1.0)
→
Bpy(1.0)
Ru(0.6), Bpy(0.4)
Ru(0.6), Bpy(0.4)
Ru(0.6), Bpy(0.4)
Ru(0.6), Bpy(0.4)
243
→
→
→
→
→
Energy
Ru(0.7)
O-Bpy(0.9)
Ru(0.7)
Bpy(0.6),O-Bpy(0.4)
Ru(0.7)
Ru(0.7)
Bpy(0.9),O-Bpy(0.1)
Bpy(0.5),O-Bpy(0.5)
Ru(0.8)
Ru(0.8)
Ru(0.8)
Ru(0.8)
Bpy(1.0)
Bpy(1.0)
Ru(0.8)
Ru(0.8)
Ru(0.8)
Ru(0.8)
17.2
18.2
18.5
19.0
19.3
3
MLLCT
d-d
3
ILCT
3
d-d
3
ILCT
3
d-d
3
d-d
3
17.6
18.4
3
18.6
19.9
3
20.3
3
ILCT
MLMCT
3
MLMCT
3
MLMCT
3
MLMCT
3
17.7
18.4
3
18.4
19.8
3
19.8
MLLCT
ILCT
3
MLLCT
ILCT
ILCT
MLMCT
3
MLMCT
3
MLMCT
3
MLMCT
3
APPENDIX B (continued)
243
O-Bpy
Dimer
State
APPENDIX B (continued)
Crystal Structure Reports
[Ru(bpy)(Obpy)]2+
Atomic coordinates (x 104) and equivalent isotropic displacement parameters(Ǻ2 x 103)
U(eq) is defined as one third of the trace of the orthogonalized Uij tensor.
_________________________________________________________
x
y
z
U(eq)
_________________________________________________________
C(1)
-796(5)
6803(2)
6283(4)
29(1)
C(2)
-1955(5)
6728(2)
5744(4)
31(1)
C(3)
-2334(5)
6232(2)
5498(4)
33(1)
C(4)
-1545(5)
5818(2)
5787(4)
33(1)
C(5)
-393(5)
5911(2)
6310(4)
26(1)
C(6)
545(5)
5495(2)
6595(4)
24(1)
C(7)
281(5)
4964(2)
6490(4)
33(1)
C(8)
1226(5)
4598(2)
6749(4)
33(1)
C(9)
2422(5)
4774(2)
7049(4)
32(1)
C(10)
2641(5)
5302(2)
7122(4)
29(1)
C(11)
3195(5)
6480(2)
5258(4)
29(1)
C(12)
3998(5)
6708(2)
4503(4)
32(1)
C(13)
4240(5)
7240(2)
4557(4)
33(1)
C(14)
3648(5)
7534(2)
5361(4)
30(1)
C(15)
2832(4)
7294(2)
6096(4)
23(1)
C(16)
2135(4)
7571(2)
6980(4)
23(1)
C(17)
2084(5)
8114(2)
7032(4)
32(1)
C(18)
1319(5)
8346(2)
7809(5)
37(1)
C(19)
632(5)
8033(2)
8499(4)
33(1)
C(20)
717(5)
7487(2)
8454(4)
26(1)
C(21)
-55(5)
7193(2)
9308(4)
36(1)
C(22)
-759(5)
6668(2)
9058(4)
33(1)
C(23)
44(5)
6209(2)
9410(4)
31(1)
C(24)
-267(5)
5886(2)
10278(4)
38(1)
C(25)
636(6)
5539(2)
10686(5)
46(2)
C(26)
1877(6)
5561(2)
10291(4)
39(1)
C(27)
2154(5)
5901(2)
9430(4)
31(1)
C(28)
3463(5)
6034(2)
9054(4)
29(1)
C(29)
4589(5)
5865(2)
9570(4)
37(1)
C(30)
5758(6)
6038(2)
9187(5)
44(2)
C(31)
5791(5)
6383(2)
8338(5)
39(1)
C(32)
4653(5)
6538(2)
7852(4)
31(1)
F(1)
5142(3)
4444(1)
6333(3)
54(1)
F(2)
6742(3)
4225(1)
7500(3)
61(1)
244
APPENDIX B (continued)
F(3)
F(4)
F(5)
F(6)
F(7)
F(8)
F(9)
F(10)
F(11)
F(12)
N(1)
N(2)
N(3)
N(4)
N(5)
N(6)
P(1)
P(2)
Ru(1)
5765(3)
5295(1)
6416(3)
51(1)
5328(3)
4855(1)
7977(3)
51(1)
7392(3)
5075(1)
7568(3)
48(1)
7204(3)
4659(1)
5935(3)
55(1)
1632(3)
3023(2)
8225(3)
70(1)
2972(3)
3708(1)
8470(3)
59(1)
3377(3)
2926(1)
9242(2)
46(1)
2873(4)
3326(2)
6823(3)
79(1)
3272(5)
2542(1)
7597(3)
98(2)
4622(3)
3218(2)
7868(3)
76(1)
-7(3)
6410(2)
6580(3)
21(1)
1717(4)
5669(2)
6950(3)
24(1)
2623(4)
6764(2)
6059(3)
23(1)
1504(4)
7256(2)
7713(3)
23(1)
1201(4)
6180(2)
8926(3)
27(1)
3489(4)
6368(2)
8192(3)
26(1)
6254(2)
4759(1)
6951(1)
41(1)
3126(1)
3122(1)
8018(1)
35(1)
1737(1)
6460(1)
7405(1)
23(1)
_________________________________________________________
Anisotropic displacement parameters (Ǻ2 x 103)
The anisotropic displacement factor exponent takes the form:
-2 π2 [ h2 a*2 U11 + ... + 2 h k a* b* U12 ]
___________________________________________________________________
U11
U22
U33
U23
U13
___________________________________________________________________
C(1)
35(3)
27(3)
23(3)
5(2)
3(2)
C(2)
35(3)
31(3)
27(3)
6(3)
2(3)
C(3)
29(3)
41(3)
28(3)
4(3)
-1(3)
C(4)
34(3)
30(3)
33(3)
0(3)
-2(3)
C(5)
29(3)
29(3)
20(3)
1(2)
10(2)
C(6)
30(3)
26(3)
18(3)
-2(2)
7(2)
C(7)
30(3)
29(3)
39(3)
-2(3)
4(3)
C(8)
38(3)
25(3)
37(3)
0(3)
9(3)
C(9)
34(3)
22(3)
40(4)
1(3)
7(3)
C(10)
33(3)
26(3)
27(3)
-2(2)
-1(2)
C(11)
35(3)
27(3)
25(3)
-3(3)
-2(2)
C(12)
33(3)
37(3)
27(3)
-4(3)
8(3)
C(13)
35(3)
40(3)
24(3)
5(3)
9(3)
C(14)
30(3)
26(3)
33(3)
3(3)
0(3)
C(15)
23(3)
20(3)
26(3)
3(2)
-6(2)
245
U12
6(2)
6(3)
-1(3)
-5(3)
-2(2)
-2(2)
-5(3)
0(3)
8(2)
2(2)
0(3)
1(3)
-3(3)
-3(2)
-2(2)
APPENDIX B (continued)
C(16)
21(3)
27(3)
23(3)
-3(2)
-3(2)
-3(2)
C(17)
33(3)
28(3)
33(3)
1(3)
-1(3)
-6(3)
C(18)
39(3)
26(3)
48(4)
-5(3)
4(3)
2(3)
C(19)
29(3)
36(3)
32(3)
-10(3)
8(3)
5(3)
C(20)
26(3)
30(3)
22(3)
-5(2)
-3(2)
2(2)
C(21)
43(3)
35(3)
31(3)
-7(3)
10(3)
3(3)
C(22)
33(3)
37(3)
31(3)
-3(3)
12(3)
1(3)
C(23)
32(3)
32(3)
28(3)
-2(3)
2(3)
-4(3)
C(24)
41(3)
37(3)
35(4)
-1(3)
11(3)
-5(3)
C(25)
59(4)
39(4)
39(4)
10(3)
14(3)
-7(3)
C(26)
48(4)
34(3)
36(4)
6(3)
3(3)
4(3)
C(27)
44(3)
26(3)
21(3)
-5(3)
1(3)
1(3)
C(28)
36(3)
28(3)
23(3)
-6(3)
2(3)
1(2)
C(29)
48(4)
33(3)
31(3)
2(3)
-3(3)
2(3)
C(30)
35(4)
49(4)
50(4)
0(3)
-10(3)
0(3)
C(31)
22(3)
45(4)
51(4)
2(3)
-5(3)
-2(3)
C(32)
31(3)
36(3)
26(3)
-1(3)
3(2)
-2(3)
F(1)
41(2)
52(2)
67(2)
-13(2)
-1(2)
-6(2)
F(2)
57(2)
33(2)
92(3)
7(2)
-12(2)
6(2)
F(3)
58(2)
41(2)
55(2)
9(2)
-7(2)
4(2)
F(4)
49(2)
51(2)
53(2)
4(2)
12(2)
2(2)
F(5)
46(2)
39(2)
57(2)
-2(2)
-5(2)
-2(2)
F(6)
47(2)
55(2)
63(2)
-21(2)
16(2)
-9(2)
F(7)
47(2)
90(3)
74(3)
13(2)
-11(2)
-17(2)
F(8)
87(3)
33(2)
58(2)
3(2)
17(2)
4(2)
F(9)
53(2)
54(2)
32(2)
11(2)
7(2)
5(2)
F(10)
123(3)
77(3)
35(2)
17(2)
-14(2)
-9(2)
F(11)
192(5)
38(2)
64(3)
-12(2)
57(3)
8(3)
F(12)
47(2)
110(3)
73(3)
35(2)
27(2)
9(2)
N(1)
25(2)
20(2)
19(2)
1(2)
5(2)
1(2)
N(2)
25(2)
24(2)
22(2)
1(2)
4(2)
0(2)
N(3)
24(2)
23(2)
21(2)
-1(2)
-1(2)
1(2)
N(4)
22(2)
23(2)
25(2)
-4(2)
0(2)
1(2)
N(5)
33(3)
23(2)
25(3)
-1(2)
7(2)
-1(2)
N(6)
28(2)
27(2)
22(2)
-2(2)
4(2)
2(2)
P(1)
38(1)
32(1)
54(1)
-1(1)
1(1)
1(1)
P(2)
44(1)
32(1)
27(1)
4(1)
7(1)
4(1)
Ru(1)
24(1)
22(1)
22(1)
-2(1)
3(1)
1(1)
______________________________________________________________________________
246
APPENDIX B (continued)
Bond lengths [Ǻ]
____________________________________________________________________
C(1)-N(1)
1.339(6)
C(20)-C(21)
1.513(7)
C(1)-C(2)
1.379(7)
C(21)-C(22)
1.548(7)
C(1)-H(1)
0.9300
C(21)-H(21A)
0.9700
C(2)-C(3)
1.352(7)
C(21)-H(21B)
0.9700
C(2)-H(2)
0.9300
C(22)-C(23)
1.492(7)
C(3)-C(4)
1.376(7)
C(22)-H(22A)
0.9700
C(3)-H(3)
0.9300
C(22)-H(22B)
0.9700
C(4)-C(5)
1.370(7)
C(23)-N(5)
1.340(6)
C(4)-H(4)
0.9300
C(23)-C(24)
1.380(7)
C(5)-N(1)
1.365(6)
C(24)-C(25)
1.375(7)
C(5)-C(6)
1.477(7)
C(24)-H(24)
0.9300
C(6)-N(2)
1.360(6)
C(25)-C(26)
1.375(7)
C(6)-C(7)
1.380(6)
C(25)-H(25)
0.9300
C(7)-C(8)
1.384(7)
C(26)-C(27)
1.390(7)
C(7)-H(7)
0.9300
C(26)-H(26)
0.9300
C(8)-C(9)
1.364(7)
C(27)-N(5)
1.360(6)
C(8)-H(8)
0.9300
C(27)-C(28)
1.471(7)
C(9)-C(10)
1.362(6)
C(28)-N(6)
1.352(6)
C(9)-H(9)
0.9300
C(28)-C(29)
1.390(7)
C(10)-N(2)
1.350(6)
C(29)-C(30)
1.371(7)
C(10)-H(10)
0.9300
C(29)-H(29)
0.9300
C(11)-N(3)
1.353(6)
C(30)-C(31)
1.356(7)
C(11)-C(12)
1.371(7)
C(30)-H(30)
0.9300
C(11)-H(11)
0.9300
C(31)-C(32)
1.375(7)
C(12)-C(13)
1.375(7)
C(31)-H(31)
0.9300
C(12)-H(12)
0.9300
C(32)-N(6)
1.346(6)
C(13)-C(14)
1.378(7)
C(32)-H(32)
0.9300
C(13)-H(13)
0.9300
F(1)-P(1)
1.589(3)
C(14)-C(15)
1.377(6)
F(2)-P(1)
1.593(3)
C(14)-H(14)
0.9300
F(3)-P(1)
1.590(3)
C(15)-N(3)
1.363(6)
F(4)-P(1)
1.599(3)
C(15)-C(16)
1.478(7)
F(5)-P(1)
1.610(3)
C(16)-N(4)
1.367(6)
F(6)-P(1)
1.607(3)
C(16)-C(17)
1.380(6)
F(7)-P(2)
1.588(4)
C(17)-C(18)
1.371(7)
F(8)-P(2)
1.594(3)
C(17)-H(17)
0.9300
F(9)-P(2)
1.595(3)
C(18)-C(19)
1.361(7)
F(10)-P(2)
1.570(4)
C(18)-H(18)
0.9300
F(11)-P(2)
1.566(4)
C(19)-C(20)
1.391(7)
F(12)-P(2)
1.578(4)
C(19)-H(19)
0.9300
N(1)-Ru(1)
2.068(4)
C(20)-N(4)
1.354(6)
N(2)-Ru(1)
2.082(4)
247
APPENDIX B (continued)
N(3)-Ru(1)
N(4)-Ru(1)
N(5)-Ru(1)
N(6)-Ru(1)
2.038(4)
2.070(4)
2.067(4)
2.062(4)
Bond angles [deg]
________________________________________________________________________________
N(1)-C(1)-C(2)
123.7(5)
C(13)-C(12)-H(12)
120.3
N(1)-C(1)-H(1)
118.2
C(12)-C(13)-C(14)
118.9(5)
C(2)-C(1)-H(1)
118.2
C(12)-C(13)-H(13)
120.5
C(3)-C(2)-C(1)
119.1(5)
C(14)-C(13)-H(13)
120.5
C(3)-C(2)-H(2)
120.5
C(15)-C(14)-C(13)
120.1(5)
C(1)-C(2)-H(2)
120.5
C(15)-C(14)-H(14)
119.9
C(2)-C(3)-C(4)
118.8(5)
C(13)-C(14)-H(14)
119.9
C(2)-C(3)-H(3)
120.6
N(3)-C(15)-C(14)
120.8(4)
C(4)-C(3)-H(3)
120.6
N(3)-C(15)-C(16)
114.5(4)
C(5)-C(4)-C(3)
120.1(5)
C(14)-C(15)-C(16)
124.7(4)
C(5)-C(4)-H(4)
119.9
N(4)-C(16)-C(17)
122.3(5)
C(3)-C(4)-H(4)
119.9
N(4)-C(16)-C(15)
115.9(4)
N(1)-C(5)-C(4)
121.7(5)
C(17)-C(16)-C(15)
121.8(5)
N(1)-C(5)-C(6)
114.5(4)
C(18)-C(17)-C(16)
118.9(5)
C(4)-C(5)-C(6)
123.8(5)
C(18)-C(17)-H(17)
120.5
N(2)-C(6)-C(7)
121.5(5)
C(16)-C(17)-H(17)
120.5
N(2)-C(6)-C(5)
115.3(4)
C(19)-C(18)-C(17)
118.8(5)
C(7)-C(6)-C(5)
123.1(5)
C(19)-C(18)-H(18)
120.6
C(6)-C(7)-C(8)
119.5(5)
C(17)-C(18)-H(18)
120.6
C(6)-C(7)-H(7)
120.2
C(18)-C(19)-C(20)
121.6(5)
C(8)-C(7)-H(7)
120.2
C(18)-C(19)-H(19)
119.2
C(9)-C(8)-C(7)
118.8(5)
C(20)-C(19)-H(19)
119.2
C(9)-C(8)-H(8)
120.6
N(4)-C(20)-C(19)
119.7(5)
C(7)-C(8)-H(8)
120.6
N(4)-C(20)-C(21)
124.7(4)
C(10)-C(9)-C(8)
119.4(5)
C(19)-C(20)-C(21)
115.5(4)
C(10)-C(9)-H(9)
120.3
C(20)-C(21)-C(22)
122.5(4)
C(8)-C(9)-H(9)
120.3
C(20)-C(21)-H(21A)
106.7
N(2)-C(10)-C(9)
123.3(5)
C(22)-C(21)-H(21A)
106.7
N(2)-C(10)-H(10)
118.3
C(20)-C(21)-H(21B)
106.7
C(9)-C(10)-H(10)
118.3
C(22)-C(21)-H(21B)
106.7
N(3)-C(11)-C(12)
122.0(5)
H(21A)-C(21)-H(21B) 106.6
N(3)-C(11)-H(11)
119.0
C(23)-C(22)-C(21)
110.7(4)
C(12)-C(11)-H(11)
119.0
C(23)-C(22)-H(22A)
109.5
C(11)-C(12)-C(13)
119.5(5)
C(21)-C(22)-H(22A)
109.5
C(11)-C(12)-H(12)
120.3
C(23)-C(22)-H(22B)
109.5
248
APPENDIX B (continued)
C(21)-C(22)-H(22B)
H(22A)-C(22)-H(22B)
N(5)-C(23)-C(24)
N(5)-C(23)-C(22)
C(24)-C(23)-C(22)
C(25)-C(24)-C(23)
C(25)-C(24)-H(24)
C(23)-C(24)-H(24)
C(26)-C(25)-C(24)
C(26)-C(25)-H(25)
C(24)-C(25)-H(25)
C(25)-C(26)-C(27)
C(25)-C(26)-H(26)
C(27)-C(26)-H(26)
N(5)-C(27)-C(26)
N(5)-C(27)-C(28)
C(26)-C(27)-C(28)
N(6)-C(28)-C(29)
N(6)-C(28)-C(27)
C(29)-C(28)-C(27)
C(30)-C(29)-C(28)
C(30)-C(29)-H(29)
C(28)-C(29)-H(29)
C(31)-C(30)-C(29)
C(31)-C(30)-H(30)
C(29)-C(30)-H(30)
C(30)-C(31)-C(32)
C(30)-C(31)-H(31)
C(32)-C(31)-H(31)
N(6)-C(32)-C(31)
N(6)-C(32)-H(32)
C(31)-C(32)-H(32)
C(1)-N(1)-C(5)
C(1)-N(1)-Ru(1)
C(5)-N(1)-Ru(1)
C(10)-N(2)-C(6)
C(10)-N(2)-Ru(1)
C(6)-N(2)-Ru(1)
C(11)-N(3)-C(15)
C(11)-N(3)-Ru(1)
C(15)-N(3)-Ru(1)
C(20)-N(4)-C(16)
C(20)-N(4)-Ru(1)
109.5
108.1
121.2(5)
114.4(4)
123.7(5)
119.9(5)
120.0
120.0
118.8(5)
120.6
120.6
119.1(5)
120.5
120.5
121.0(5)
113.9(4)
124.8(5)
121.8(5)
114.1(4)
124.0(5)
119.0(5)
120.5
120.5
119.5(5)
120.3
120.3
119.4(5)
120.3
120.3
122.7(5)
118.6
118.6
116.6(4)
128.1(3)
115.4(3)
117.1(4)
128.0(3)
114.0(3)
118.7(4)
125.5(3)
114.8(3)
118.4(4)
127.9(3)
C(16)-N(4)-Ru(1)
C(23)-N(5)-C(27)
C(23)-N(5)-Ru(1)
C(27)-N(5)-Ru(1)
C(32)-N(6)-C(28)
C(32)-N(6)-Ru(1)
C(28)-N(6)-Ru(1)
F(1)-P(1)-F(3)
F(1)-P(1)-F(2)
F(3)-P(1)-F(2)
F(1)-P(1)-F(4)
F(3)-P(1)-F(4)
F(2)-P(1)-F(4)
F(1)-P(1)-F(6)
F(3)-P(1)-F(6)
F(2)-P(1)-F(6)
F(4)-P(1)-F(6)
F(1)-P(1)-F(5)
F(3)-P(1)-F(5)
F(2)-P(1)-F(5)
F(4)-P(1)-F(5)
F(6)-P(1)-F(5)
F(11)-P(2)-F(10)
F(11)-P(2)-F(12)
F(10)-P(2)-F(12)
F(11)-P(2)-F(7)
F(10)-P(2)-F(7)
F(12)-P(2)-F(7)
F(11)-P(2)-F(8)
F(10)-P(2)-F(8)
F(12)-P(2)-F(8)
F(7)-P(2)-F(8)
F(11)-P(2)-F(9)
F(10)-P(2)-F(9)
F(12)-P(2)-F(9)
F(7)-P(2)-F(9)
F(8)-P(2)-F(9)
N(3)-Ru(1)-N(6)
N(3)-Ru(1)-N(5)
N(6)-Ru(1)-N(5)
N(3)-Ru(1)-N(1)
N(6)-Ru(1)-N(1)
N(5)-Ru(1)-N(1)
249
113.3(3)
118.4(4)
128.4(4)
112.9(3)
117.5(4)
127.3(3)
114.4(3)
90.31(18)
90.02(19)
179.4(2)
90.87(18)
90.07(18)
89.45(19)
89.82(18)
90.68(19)
89.8(2)
179.0(2)
179.3(2)
89.84(17)
89.83(18)
89.79(18)
89.51(18)
91.1(2)
90.7(2)
90.1(2)
89.9(2)
92.3(2)
177.5(2)
178.9(2)
89.9(2)
89.7(2)
89.6(2)
90.0(2)
178.8(2)
90.06(18)
87.53(18)
88.95(18)
91.25(15)
168.14(16)
77.31(16)
91.40(14)
169.93(14)
100.41(15)
APPENDIX B (continued)
N(3)-Ru(1)-N(4)
N(6)-Ru(1)-N(4)
N(5)-Ru(1)-N(4)
N(1)-Ru(1)-N(4)
N(3)-Ru(1)-N(2)
80.18(15)
97.34(15)
98.02(16)
92.68(15)
98.87(15)
N(6)-Ru(1)-N(2)
N(5)-Ru(1)-N(2)
N(1)-Ru(1)-N(2)
N(4)-Ru(1)-N(2)
91.37(15)
84.67(15)
78.63(15)
171.25(15)
[(Ru(bpy)2)2Obpy]4+
Atomic coordinates (x 104) and equivalent isotropic displacement parameters(Ǻ2 x 103)
U(eq) is defined as one third of the trace of the orthogonalized Uij tensor.
__________________________________________________________
x
y
z
U(eq)
__________________________________________________________
C(1)
8528(5)
2792(5)
861(4)
24(2)
C(2)
8795(6)
3131(6)
398(4)
30(3)
C(3)
8558(6)
3776(6)
201(5)
42(3)
C(4)
8045(6)
4061(6)
467(5)
39(3)
C(5)
7765(5)
3685(5)
918(4)
24(2)
C(6)
7181(6)
3910(5)
1199(4)
25(2)
C(7)
6828(6)
4522(5)
1024(5)
30(3)
C(8)
6241(6)
4646(6)
1285(5)
34(3)
C(9)
6024(6)
4184(6)
1726(5)
34(3)
C(10)
6405(5)
3604(5)
1884(4)
24(2)
C(11)
5991(5)
2203(6)
465(4)
27(2)
C(12)
5531(6)
1830(6)
-126(5)
37(3)
C(13)
5716(6)
1204(6)
-346(5)
35(3)
C(14)
6357(6)
941(5)
28(5)
33(3)
C(15)
6800(6)
1327(5)
630(5)
23(2)
C(16)
7481(6)
1061(5)
1066(4)
21(2)
C(17)
7771(6)
452(6)
940(5)
29(3)
C(18)
8389(6)
254(6)
1391(5)
37(3)
C(19)
8719(6)
677(6)
1961(5)
32(3)
C(20)
8421(6)
1308(5)
2081(5)
28(2)
C(21)
5943(5)
1511(5)
1989(4)
25(2)
C(22)
5497(6)
1189(6)
2369(5)
35(3)
C(23)
5819(7)
1308(7)
3012(5)
48(3)
C(24)
6564(7)
1809(7)
3264(5)
50(3)
C(25)
7000(6)
2147(6)
2875(5)
29(3)
C(26)
7784(6)
2699(5)
3099(4)
24(2)
C(27)
8107(6)
3013(6)
3724(5)
40(3)
C(28)
8867(6)
3519(6)
3936(5)
40(3)
C(29)
9279(5)
3679(5)
3501(4)
25(2)
250
APPENDIX B (continued)
C(30)
C(31)
C(32)
C(33)
C(34)
C(35)
C(36)
C(37)
C(38)
C(39)
C(40)
C(41)
C(42)
C(43)
C(44)
C(45)
C(46)
C(47)
C(48)
C(49)
C(50)
C(51)
C(52)
C(53)
C(54)
C(55)
C(56)
C(57)
C(58)
C(59)
C(60)
C(61)
C(62)
C(63)
C(64)
C(65)
C(66)
C(67)
C(68)
C(69)
C(70)
C(71)
C(72)
8936(5)
9413(5)
10337(5)
10799(5)
10444(6)
10830(6)
11549(6)
11891(5)
12676(6)
13031(6)
13809(7)
14190(6)
13795(6)
11471(5)
11299(6)
11702(6)
12301(6)
12468(5)
13122(6)
13633(6)
14228(6)
14318(6)
13790(6)
11323(5)
11044(6)
11238(6)
11705(6)
11952(5)
12462(5)
12714(6)
13211(6)
13445(6)
13176(5)
-3880(5)
-4417(6)
-4372(6)
-3762(6)
-3216(6)
-2572(6)
-2371(6)
-1770(6)
-1351(6)
-1555(5)
3342(5)
3504(5)
3738(5)
3788(5)
3989(5)
3983(5)
3749(6)
3553(5)
3346(5)
3131(5)
2995(5)
3096(5)
3260(5)
1890(5)
1130(5)
879(6)
1394(6)
2158(5)
2755(6)
2613(6)
3225(7)
3948(7)
4047(6)
3393(5)
3631(6)
4396(6)
4904(5)
4627(5)
5113(6)
5900(5)
6301(6)
5914(6)
5136(5)
7288(5)
6916(6)
6198(7)
5885(6)
6285(5)
6000(5)
5333(5)
5092(5)
5541(6)
6217(5)
251
2872(4)
2408(4)
2713(4)
2238(4)
1630(5)
1184(4)
1326(4)
1937(4)
2116(5)
1695(5)
1907(5)
2544(5)
2959(5)
2930(4)
3000(5)
3551(5)
4019(5)
3904(4)
4363(4)
4944(4)
5310(5)
5117(5)
4540(4)
4227(4)
4704(4)
4904(5)
4613(4)
4133(4)
3812(4)
3940(5)
3617(5)
3199(5)
3089(4)
2641(4)
2931(5)
3108(5)
3010(5)
2725(4)
2601(4)
2793(4)
2636(4)
2285(5)
2116(4)
23(2)
21(2)
25(2)
25(2)
31(3)
30(3)
32(3)
21(2)
23(2)
28(2)
40(3)
34(3)
27(2)
22(2)
28(2)
36(3)
32(3)
20(2)
24(2)
32(3)
42(3)
43(3)
28(2)
20(2)
28(2)
31(3)
25(2)
17(2)
22(2)
30(2)
36(3)
34(3)
24(2)
26(2)
35(3)
37(3)
33(3)
21(2)
20(2)
25(2)
30(3)
34(3)
24(2)
APPENDIX B (continued)
C(73)
C(74)
C(75)
C(76)
C(77)
C(78)
C(79)
C(80)
C(81)
C(82)
C(83)
C(84)
C(85)
C(86)
C(87)
C(88)
C(89)
C(90)
C(91)
C(92)
C(93)
C(94)
C(95)
C(96)
C(97)
C(98)
C(99)
C(100)
C(101)
C(102)
C(103)
C(104)
C(105)
C(106)
C(107)
C(108)
C(109)
C(110)
C(111)
C(112)
C(113)
C(114)
C(115)
-1399(5)
-1114(6)
-1299(6)
-1742(6)
-2010(5)
-2527(5)
-2766(6)
-3263(6)
-3520(6)
-3272(6)
-3933(6)
-4383(6)
-4011(7)
-3224(6)
-2813(6)
-2014(6)
-1659(6)
-936(6)
-559(6)
-910(5)
-453(5)
475(5)
912(5)
545(6)
926(6)
1649(6)
2012(6)
2776(6)
3119(7)
3887(7)
4290(6)
3907(6)
3470(6)
3857(6)
3699(7)
3132(6)
2761(6)
2200(6)
1937(6)
1452(6)
1212(6)
1462(5)
1493(5)
7716(5)
8077(6)
8755(6)
9076(5)
8698(5)
8982(5)
9669(5)
9866(6)
9383(6)
8711(6)
6594(5)
6258(6)
6342(6)
6768(6)
7127(5)
7670(5)
7955(6)
8496(6)
8702(5)
8374(5)
8547(5)
8762(5)
8822(5)
9017(6)
9022(6)
8807(6)
8628(5)
8390(6)
8167(7)
8012(6)
8100(5)
8286(5)
10161(5)
10921(6)
11312(6)
10936(6)
10170(6)
9701(6)
9975(6)
9493(7)
8726(6)
8474(6)
6984(5)
252
3500(4)
4119(4)
4226(5)
3737(4)
3131(4)
2578(4)
2589(5)
2050(5)
1498(5)
1499(5)
1039(5)
424(5)
-43(5)
123(5)
727(4)
912(4)
467(5)
665(5)
1301(5)
1742(4)
2435(4)
2597(4)
3292(4)
3727(5)
4362(5)
4562(5)
4114(5)
4290(5)
4889(5)
5052(5)
4610(5)
4015(5)
3653(5)
3715(5)
3200(6)
2633(5)
2599(5)
2020(4)
1431(5)
905(5)
957(5)
1549(4)
2774(4)
23(2)
27(2)
31(3)
27(2)
20(2)
19(2)
26(2)
35(3)
34(3)
27(2)
28(2)
32(3)
42(3)
40(3)
27(2)
24(2)
29(3)
37(3)
27(3)
20(2)
22(2)
23(2)
21(2)
33(3)
42(3)
41(3)
29(2)
33(3)
54(3)
46(3)
36(3)
29(2)
27(2)
35(3)
42(3)
32(3)
27(2)
24(2)
35(3)
40(3)
32(3)
27(2)
23(2)
APPENDIX B (continued)
C(116)
C(117)
C(118)
C(119)
C(120)
C(121)
C(122)
C(123)
C(124)
F(1)
F(2)
F(3)
F(4)
F(5)
F(6)
F(7)
F(8)
F(9)
F(10)
F(11)
F(12)
F(13)
F(14)
F(15)
F(16)
F(17)
F(18)
F(19)
F(20)
F(21)
F(22)
F(23)
F(24)
F(25)
F(26)
F(27)
F(28)
F(29)
F(30)
F(31)
F(32)
F(33)
F(34)
1223(6)
1572(7)
2217(7)
2482(5)
3188(6)
3698(6)
4387(7)
4559(6)
4033(6)
9556(4)
9691(4)
10606(3)
9736(4)
9578(4)
8674(4)
9359(6)
9683(4)
10502(5)
9423(5)
9734(4)
8602(4)
3001(4)
3672(4)
4378(3)
4458(3)
3785(4)
3091(3)
6831(4)
6829(4)
5448(3)
6084(4)
5460(4)
6200(4)
2994(4)
4653(4)
3325(5)
3790(4)
3841(5)
4326(4)
480(5)
1313(4)
544(5)
-592(4)
6232(6)
5977(6)
6470(6)
7220(5)
7764(5)
7593(6)
8141(6)
8839(6)
8985(6)
617(3)
622(3)
1467(3)
1884(3)
1880(3)
1061(4)
5547(4)
5602(3)
6390(4)
6814(4)
6870(3)
6025(4)
500(4)
1308(4)
739(3)
2001(3)
1188(3)
1762(4)
4731(4)
3540(4)
3226(3)
4235(4)
4415(3)
3735(5)
5707(4)
5184(4)
4574(4)
5383(4)
5503(5)
6291(4)
2068(4)
1655(3)
836(3)
1170(4)
253
2496(5)
2104(6)
1980(5)
2262(4)
2206(4)
1871(5)
1882(5)
2222(5)
2539(4)
4396(3)
3420(3)
4238(3)
3441(3)
4419(3)
3600(3)
228(3)
1289(3)
849(4)
276(3)
1347(3)
730(3)
504(3)
-15(3)
771(3)
918(3)
1434(3)
656(3)
4123(4)
4400(3)
3982(3)
4724(3)
3715(3)
3385(3)
1003(3)
1368(3)
1078(4)
479(3)
1901(3)
1302(4)
609(3)
1443(3)
576(3)
653(3)
40(3)
51(3)
43(3)
21(2)
23(2)
30(2)
37(3)
31(3)
27(2)
53(2)
54(2)
49(2)
55(2)
57(2)
60(2)
90(3)
52(2)
89(3)
83(3)
51(2)
64(2)
59(2)
75(2)
57(2)
47(2)
47(2)
57(2)
93(3)
53(2)
53(2)
69(2)
64(2)
92(3)
80(2)
68(2)
91(3)
66(2)
100(3)
79(2)
70(2)
58(2)
66(2)
69(2)
APPENDIX B (continued)
F(35)
F(36)
F(37)
F(38)
F(39)
F(40)
F(41)
F(42)
F(43)
F(44)
F(45)
F(46)
F(47)
F(48)
N(1)
N(2)
N(3)
N(4)
N(5)
N(6)
N(7)
N(8)
N(9)
N(10)
N(11)
N(12)
N(13)
N(14)
N(15)
N(16)
N(17)
N(18)
N(19)
N(20)
N(21)
N(22)
N(23)
N(24)
P(1)
P(2)
P(3)
P(4)
P(5)
245(4)
173(4)
7008(4)
6269(5)
5691(4)
5337(4)
6645(5)
6060(5)
167(4)
1251(3)
233(4)
-688(3)
379(3)
330(3)
8027(4)
6965(4)
6618(4)
7824(5)
6686(4)
8171(4)
11529(4)
13030(4)
12044(4)
13204(4)
11754(4)
12710(4)
-3298(4)
-2132(4)
-1838(4)
-2792(4)
-3164(4)
-1657(4)
1668(4)
3148(4)
2956(4)
1948(4)
2100(5)
3357(5)
9638(2)
9553(2)
3730(2)
6150(2)
3819(2)
738(3)
1979(4)
9205(5)
9400(6)
8572(4)
9681(4)
10299(5)
9437(5)
6952(4)
6632(3)
5710(3)
6145(3)
5810(3)
7060(3)
3042(4)
3449(4)
1955(4)
1506(4)
1984(4)
2890(4)
3610(4)
3377(4)
2417(4)
3460(4)
3860(4)
4733(4)
6986(4)
6466(4)
8020(4)
8508(4)
7013(4)
7881(4)
8676(4)
8403(4)
9782(4)
8940(4)
7470(4)
8464(5)
1258(2)
6213(2)
1255(2)
3976(2)
5425(2)
254
1490(3)
1524(3)
4445(4)
3466(4)
3989(4)
3854(3)
4281(5)
4814(3)
3464(3)
4165(3)
3507(3)
3861(3)
4552(2)
4520(3)
1128(3)
1618(3)
851(3)
1637(3)
2230(3)
2654(3)
2397(3)
2748(4)
3374(3)
4156(4)
3934(3)
3398(3)
2527(3)
2277(3)
3012(3)
2034(3)
1194(3)
1553(3)
3480(3)
3841(3)
3124(4)
2073(3)
2649(4)
2535(4)
3919(1)
780(2)
710(1)
4057(2)
1194(1)
51(2)
56(2)
95(3)
122(4)
77(2)
62(2)
144(5)
95(3)
52(2)
48(2)
49(2)
43(2)
41(2)
44(2)
21(2)
20(2)
17(2)
22(2)
19(2)
18(2)
20(2)
18(2)
21(2)
21(2)
14(2)
17(2)
17(2)
22(2)
16(2)
20(2)
20(2)
20(2)
21(2)
18(2)
23(2)
21(2)
26(2)
24(2)
33(1)
50(1)
33(1)
41(1)
38(1)
APPENDIX B (continued)
P(6)
P(7)
P(8)
Ru(1)
Ru(2)
Ru(3)
Ru(4)
363(2)
1405(2)
1047(1)
41(1)
6177(2)
9455(2)
4147(2)
48(1)
281(2)
6383(2)
4016(1)
31(1)
7409(1)
2478(1)
1711(1)
18(1)
12354(1)
3568(1)
3324(1)
18(1)
-2454(1)
7484(1)
2099(1)
18(1)
2502(1)
8617(1)
2956(1)
19(1)
_________________________________________________________
Anisotropic displacement parameters (Ǻ2 x 103)
The anisotropic displacement factor exponent takes the form:
-2 π2 [ h2 a*2 U11 + ... + 2 h k a* b* U12 ]
__________________________________________________________________
U11
U22
U33
U23
U13
__________________________________________________________________
C(1)
18(5)
27(6)
29(6)
0(5)
13(5)
C(2)
40(7)
36(7)
21(6)
2(5)
18(5)
C(3)
49(8)
48(8)
28(7)
11(6)
17(6)
C(4)
45(7)
46(8)
30(7)
23(6)
11(6)
C(5)
23(6)
26(6)
16(5)
1(4)
-2(4)
C(6)
33(6)
20(6)
20(6)
-2(4)
6(5)
C(7)
31(6)
26(6)
32(6)
11(5)
8(5)
C(8)
34(6)
28(7)
42(7)
-4(5)
6(5)
C(9)
26(6)
30(7)
52(8)
0(5)
23(5)
C(10)
14(5)
25(6)
34(6)
4(5)
8(4)
C(11)
21(6)
33(6)
25(6)
10(5)
-1(5)
C(12)
20(6)
69(9)
21(6)
0(6)
-2(5)
C(13)
37(7)
42(8)
19(6)
-3(5)
0(5)
C(14)
39(7)
22(6)
33(7)
-7(5)
12(5)
C(15)
24(6)
19(6)
24(6)
-3(5)
8(5)
C(16)
32(6)
22(6)
11(5)
4(4)
8(4)
C(17)
31(6)
33(7)
30(6)
-1(5)
19(5)
C(18)
33(7)
38(7)
44(7)
6(6)
10(6)
C(19)
25(6)
48(8)
22(6)
6(5)
1(5)
C(20)
28(6)
22(6)
32(6)
2(5)
6(5)
C(21)
14(5)
38(7)
22(6)
14(5)
1(4)
C(22)
26(6)
36(7)
41(7)
15(5)
10(5)
C(23)
38(7)
66(9)
40(8)
25(6)
15(6)
C(24)
44(8)
90(10)
9(6)
4(6)
6(5)
C(25)
27(6)
36(7)
25(6)
15(5)
11(5)
C(26)
29(6)
37(7)
15(5)
5(4)
13(4)
C(27)
33(6)
70(9)
19(6)
-1(5)
14(5)
C(28)
38(7)
68(9)
15(6)
-1(5)
5(5)
255
U12
3(4)
10(5)
2(6)
20(6)
8(5)
3(5)
5(5)
21(5)
5(5)
5(4)
12(5)
18(6)
12(6)
-1(5)
0(5)
6(5)
11(5)
20(5)
13(5)
6(5)
11(5)
4(5)
7(6)
3(7)
4(5)
18(5)
11(6)
21(6)
APPENDIX B (continued)
C(29)
C(30)
C(31)
C(32)
C(33)
C(34)
C(35)
C(36)
C(37)
C(38)
C(39)
C(40)
C(41)
C(42)
C(43)
C(44)
C(45)
C(46)
C(47)
C(48)
C(49)
C(50)
C(51)
C(52)
C(53)
C(54)
C(55)
C(56)
C(57)
C(58)
C(59)
C(60)
C(61)
C(62)
C(63)
C(64)
C(65)
C(66)
C(67)
C(68)
C(69)
C(70)
C(71)
16(5)
25(6)
22(5)
21(5)
19(5)
30(6)
27(6)
31(6)
27(6)
25(6)
31(6)
53(8)
36(6)
36(6)
25(6)
29(6)
36(7)
35(6)
25(6)
32(6)
41(7)
32(7)
30(7)
38(6)
10(5)
27(6)
31(6)
32(6)
15(5)
19(5)
36(6)
44(7)
27(6)
24(6)
27(6)
33(6)
33(7)
42(7)
26(6)
30(6)
32(6)
50(7)
30(6)
26(6)
17(6)
21(6)
27(6)
19(6)
21(6)
39(7)
40(7)
8(5)
23(6)
26(6)
26(6)
28(6)
24(6)
16(6)
14(6)
23(6)
30(7)
17(6)
26(6)
41(7)
47(8)
48(8)
31(7)
21(6)
32(7)
38(7)
22(6)
13(5)
27(6)
15(6)
14(6)
32(7)
23(6)
17(6)
37(7)
52(8)
32(7)
24(6)
12(5)
19(6)
17(6)
29(7)
31(6)
27(6)
20(5)
22(6)
29(6)
33(7)
16(6)
16(6)
21(6)
22(6)
25(6)
52(8)
44(7)
27(6)
24(6)
33(6)
49(8)
33(7)
20(6)
21(6)
17(6)
36(7)
38(7)
14(5)
24(6)
27(6)
28(6)
26(6)
21(5)
20(6)
42(7)
50(7)
41(7)
25(6)
35(6)
41(7)
30(7)
37(7)
12(5)
19(5)
21(6)
16(6)
38(7)
256
-4(5)
-1(4)
5(4)
3(4)
6(4)
2(5)
14(5)
3(5)
-9(4)
-2(4)
-1(5)
-13(5)
1(5)
9(5)
-6(4)
-4(5)
-1(6)
11(5)
3(4)
1(5)
15(5)
-8(6)
-1(6)
9(5)
6(4)
6(5)
3(5)
2(5)
2(4)
5(5)
0(5)
-7(5)
12(6)
-2(5)
3(5)
3(5)
9(6)
22(5)
2(4)
2(4)
1(4)
-4(4)
-6(5)
-2(5)
3(5)
2(4)
3(4)
-1(5)
3(5)
-6(5)
7(5)
9(4)
12(5)
11(5)
40(6)
21(6)
18(5)
8(4)
3(5)
15(6)
11(5)
12(4)
17(5)
4(5)
-6(5)
-10(5)
4(5)
-2(4)
8(5)
14(5)
9(5)
-1(4)
6(4)
18(5)
24(6)
12(5)
12(5)
9(5)
21(5)
20(5)
26(5)
0(4)
9(4)
8(5)
-2(5)
0(5)
10(4)
14(4)
8(4)
1(4)
3(4)
-4(5)
3(5)
-8(5)
-8(4)
2(5)
1(5)
4(5)
9(5)
9(5)
3(4)
3(4)
6(5)
12(5)
5(4)
9(5)
21(5)
15(6)
11(6)
9(5)
3(4)
9(5)
11(5)
12(5)
7(4)
4(4)
5(5)
-6(5)
2(5)
1(5)
7(5)
7(5)
6(6)
11(5)
8(5)
4(4)
4(5)
11(5)
14(5)
APPENDIX B (continued)
C(72)
C(73)
C(74)
C(75)
C(76)
C(77)
C(78)
C(79)
C(80)
C(81)
C(82)
C(83)
C(84)
C(85)
C(86)
C(87)
C(88)
C(89)
C(90)
C(91)
C(92)
C(93)
C(94)
C(95)
C(96)
C(97)
C(98)
C(99)
C(100)
C(101)
C(102)
C(103)
C(104)
C(105)
C(106)
C(107)
C(108)
C(109)
C(110)
C(111)
C(112)
C(113)
C(114)
27(6)
28(6)
29(6)
33(6)
34(6)
20(5)
26(6)
29(6)
34(7)
29(6)
29(6)
32(6)
32(6)
48(8)
46(7)
39(6)
28(6)
27(6)
27(6)
17(5)
24(6)
21(5)
23(5)
21(5)
30(6)
32(7)
31(7)
29(6)
35(7)
46(8)
51(8)
33(6)
37(6)
35(6)
46(7)
63(8)
44(7)
29(6)
24(6)
32(6)
34(7)
20(6)
22(6)
29(6)
14(5)
36(7)
35(7)
24(6)
24(6)
14(6)
17(6)
20(6)
36(7)
27(6)
24(6)
31(7)
43(8)
41(7)
25(6)
28(6)
41(7)
61(8)
25(6)
20(6)
21(6)
19(6)
9(5)
33(7)
58(8)
66(9)
32(7)
36(7)
76(10)
47(8)
24(6)
15(6)
18(6)
20(6)
16(6)
21(6)
28(7)
30(7)
42(7)
75(9)
54(8)
37(7)
22(6)
25(6)
15(5)
20(6)
28(6)
16(5)
19(6)
39(7)
60(8)
40(7)
31(6)
32(6)
22(6)
23(6)
33(7)
19(6)
19(6)
19(6)
32(7)
42(7)
19(5)
31(6)
27(6)
35(6)
31(7)
37(7)
23(6)
26(6)
26(6)
37(7)
27(7)
41(7)
32(6)
33(6)
38(7)
51(8)
43(7)
33(6)
24(6)
42(7)
18(6)
24(6)
30(6)
257
7(5)
5(4)
10(5)
-4(5)
3(5)
3(4)
2(4)
3(5)
21(6)
14(6)
12(5)
9(5)
0(5)
0(5)
4(5)
0(5)
6(4)
6(5)
22(6)
14(5)
2(4)
6(4)
-1(4)
0(4)
-2(5)
-11(6)
2(5)
11(5)
19(5)
21(7)
15(6)
9(5)
0(5)
10(5)
-2(5)
5(6)
22(5)
5(5)
8(5)
21(6)
22(6)
11(5)
2(5)
15(5)
8(5)
8(4)
8(5)
13(5)
8(4)
13(4)
19(5)
24(6)
9(5)
15(5)
16(5)
-2(5)
3(6)
18(6)
10(5)
8(5)
4(5)
15(5)
14(5)
11(4)
15(4)
11(4)
17(5)
13(5)
21(6)
10(5)
14(5)
7(5)
11(6)
-2(6)
-6(5)
12(5)
16(5)
16(6)
28(7)
29(6)
23(5)
10(5)
20(6)
8(5)
8(5)
15(5)
4(5)
0(4)
5(5)
2(5)
12(5)
6(4)
0(4)
4(5)
11(5)
14(5)
8(5)
7(5)
1(5)
0(6)
5(6)
8(5)
10(5)
10(5)
18(6)
4(4)
7(4)
10(4)
1(4)
-7(4)
-6(5)
0(6)
2(6)
0(5)
8(5)
5(7)
3(6)
10(5)
-1(5)
7(5)
5(5)
4(6)
8(5)
8(5)
14(5)
19(5)
24(6)
10(5)
13(5)
APPENDIX B (continued)
C(115)
C(116)
C(117)
C(118)
C(119)
C(120)
C(121)
C(122)
C(123)
C(124)
F(1)
F(2)
F(3)
F(4)
F(5)
F(6)
F(7)
F(8)
F(9)
F(10)
F(11)
F(12)
F(13)
F(14)
F(15)
F(16)
F(17)
F(18)
F(19)
F(20)
F(21)
F(22)
F(23)
F(24)
F(25)
F(26)
F(27)
F(28)
F(29)
F(30)
F(31)
F(32)
F(33)
26(6)
42(7)
60(8)
53(8)
18(5)
24(6)
38(7)
47(7)
25(6)
28(6)
82(5)
88(5)
38(4)
63(4)
75(5)
40(4)
199(9)
74(5)
103(6)
166(8)
69(5)
70(5)
41(4)
72(5)
39(4)
39(4)
51(4)
37(4)
52(5)
37(4)
40(4)
76(5)
45(4)
74(5)
44(4)
53(4)
100(6)
66(5)
82(6)
75(5)
136(7)
46(4)
130(6)
16(6)
26(7)
12(6)
23(7)
21(6)
21(6)
25(6)
41(8)
33(7)
30(6)
46(4)
46(4)
53(4)
43(4)
46(4)
66(5)
48(5)
60(5)
87(6)
59(5)
47(4)
69(5)
67(5)
123(7)
39(4)
30(4)
62(5)
75(5)
77(6)
63(5)
42(4)
87(6)
51(4)
171(9)
120(7)
92(6)
51(5)
99(6)
198(9)
41(5)
41(4)
57(5)
40(4)
24(6)
49(8)
82(10)
54(8)
28(6)
22(6)
37(6)
37(7)
41(7)
26(6)
26(4)
31(4)
42(4)
35(4)
47(4)
60(5)
57(5)
48(4)
133(7)
58(5)
41(4)
50(5)
57(5)
24(4)
87(5)
63(4)
30(4)
57(4)
103(6)
55(4)
71(5)
43(4)
73(5)
31(4)
79(6)
78(5)
138(8)
33(4)
41(5)
122(7)
48(5)
70(5)
42(4)
258
3(4)
0(5)
-10(6)
-9(6)
8(5)
7(5)
17(5)
3(5)
14(5)
6(5)
11(3)
-8(3)
4(3)
16(3)
-14(3)
-6(4)
15(4)
30(3)
45(5)
35(4)
-3(3)
0(4)
-25(4)
2(4)
-19(4)
-15(3)
4(3)
-6(4)
56(5)
15(3)
21(3)
-8(4)
30(4)
12(5)
-18(5)
25(4)
7(5)
3(4)
21(5)
-30(4)
13(3)
0(4)
3(3)
10(4)
18(6)
38(7)
21(6)
11(5)
4(4)
17(5)
26(6)
17(5)
9(5)
20(3)
26(4)
-3(3)
-6(3)
15(4)
11(3)
76(6)
40(4)
100(6)
61(5)
32(3)
9(4)
18(3)
14(3)
17(4)
15(3)
19(3)
4(3)
-22(4)
4(3)
8(3)
6(4)
-17(3)
24(4)
13(4)
25(4)
76(6)
23(4)
37(4)
46(5)
53(5)
29(4)
47(4)
-2(4)
-1(5)
-10(6)
7(6)
5(4)
7(5)
18(5)
27(6)
10(5)
11(5)
2(4)
13(4)
6(3)
-7(3)
16(4)
-5(3)
48(5)
33(4)
44(5)
60(5)
2(3)
27(4)
-14(3)
13(5)
8(3)
-2(3)
13(3)
28(3)
-25(4)
20(3)
6(3)
39(4)
11(3)
20(5)
41(4)
48(4)
-5(4)
7(4)
48(6)
-1(4)
17(4)
-5(3)
23(4)
APPENDIX B (continued)
F(34)
F(35)
F(36)
F(37)
F(38)
F(39)
F(40)
F(41)
F(42)
F(43)
F(44)
F(45)
F(46)
F(47)
F(48)
N(1)
N(2)
N(3)
N(4)
N(5)
N(6)
N(7)
N(8)
N(9)
N(10)
N(11)
N(12)
N(13)
N(14)
N(15)
N(16)
N(17)
N(18)
N(19)
N(20)
N(21)
N(22)
N(23)
N(24)
P(1)
P(2)
P(3)
P(4)
72(5)
57(4)
75(5)
43(4)
79(6)
69(5)
41(4)
79(6)
89(6)
52(4)
33(4)
64(4)
31(3)
53(4)
46(4)
13(4)
19(4)
21(4)
37(5)
16(4)
18(4)
28(5)
18(4)
15(4)
18(4)
13(4)
12(4)
15(4)
22(4)
18(4)
15(4)
20(4)
12(4)
23(5)
17(4)
24(5)
15(4)
30(5)
18(5)
40(2)
86(3)
27(2)
35(2)
70(5)
49(4)
62(5)
156(8)
229(11)
57(5)
51(5)
82(7)
159(8)
73(5)
61(5)
50(4)
56(4)
47(4)
36(4)
31(5)
23(5)
19(5)
14(5)
20(5)
17(4)
12(4)
10(4)
19(5)
20(5)
15(4)
18(5)
18(5)
23(5)
20(5)
26(5)
20(5)
25(5)
17(5)
20(5)
20(5)
28(5)
27(5)
25(5)
30(2)
45(2)
44(2)
44(2)
43(4)
43(4)
38(4)
98(6)
67(6)
114(7)
74(5)
181(10)
39(5)
51(4)
57(4)
41(4)
40(4)
26(3)
54(4)
16(4)
16(4)
17(4)
18(5)
23(5)
16(4)
15(4)
29(5)
26(5)
25(5)
16(4)
18(4)
17(4)
19(4)
16(4)
21(5)
20(5)
25(5)
26(5)
22(5)
31(5)
21(5)
18(5)
30(5)
23(2)
41(2)
26(2)
40(2)
259
7(4)
23(3)
-3(3)
54(6)
45(7)
26(4)
16(4)
39(7)
6(5)
35(4)
13(3)
-1(3)
7(3)
11(3)
-5(3)
-1(4)
1(4)
4(4)
-2(4)
5(4)
-2(3)
0(3)
3(3)
10(4)
2(4)
2(3)
5(3)
1(3)
-3(4)
6(4)
12(4)
7(4)
7(4)
9(4)
8(4)
3(4)
4(4)
5(4)
9(4)
-1(1)
19(2)
-7(1)
15(2)
-9(4)
19(3)
15(3)
22(4)
44(5)
33(5)
-12(4)
-51(6)
15(4)
29(3)
21(3)
20(3)
11(3)
11(3)
24(3)
2(3)
3(3)
17(4)
10(4)
3(4)
4(3)
5(4)
12(4)
6(4)
8(4)
7(3)
4(3)
4(3)
2(4)
12(3)
6(4)
7(4)
9(4)
13(4)
8(4)
13(4)
5(4)
5(4)
11(4)
6(1)
37(2)
8(1)
8(1)
8(4)
2(3)
35(4)
40(5)
22(7)
26(4)
12(3)
-45(5)
39(6)
33(4)
12(3)
25(3)
3(3)
22(3)
8(3)
3(4)
4(4)
1(4)
8(4)
11(4)
2(3)
-2(3)
3(3)
0(4)
3(4)
6(3)
0(3)
1(4)
7(4)
5(4)
6(4)
2(4)
6(4)
4(4)
11(3)
8(4)
10(4)
6(4)
3(4)
-1(1)
32(2)
7(1)
3(2)
APPENDIX B (continued)
P(5)
32(2)
47(2)
39(2)
-4(2)
17(1)
11(2)
P(6)
63(2)
34(2)
27(2)
7(1)
18(2)
9(2)
P(7)
34(2)
67(3)
40(2)
22(2)
9(2)
7(2)
P(8)
31(2)
38(2)
29(2)
7(1)
13(1)
12(1)
Ru(1)
19(1)
19(1)
17(1)
2(1)
4(1)
7(1)
Ru(2)
19(1)
16(1)
18(1)
2(1)
6(1)
3(1)
Ru(3)
20(1)
18(1)
19(1)
5(1)
7(1)
6(1)
Ru(4)
21(1)
17(1)
19(1)
3(1)
7(1)
3(1)
______________________________________________________________________
Bond lengths [Ǻ]
______________________________________________________________________________
__
C(1)-N(1)
1.342(10)
C(14)-H(14)
0.9300
C(1)-C(2)
1.360(12)
C(15)-N(3)
1.355(11)
C(1)-H(1)
0.9300
C(15)-C(16)
1.483(12)
C(2)-C(3)
1.362(13)
C(16)-C(17)
1.360(12)
C(2)-H(2)
0.9300
C(16)-N(4)
1.368(10)
C(3)-C(4)
1.388(14)
C(17)-C(18)
1.363(13)
C(3)-H(3)
0.9300
C(17)-H(17)
0.9300
C(4)-C(5)
1.377(12)
C(18)-C(19)
1.348(13)
C(4)-H(4)
0.9300
C(18)-H(18)
0.9300
C(5)-N(1)
1.383(11)
C(19)-C(20)
1.400(12)
C(5)-C(6)
1.468(13)
C(19)-H(19)
0.9300
C(6)-N(2)
1.350(11)
C(20)-N(4)
1.333(11)
C(6)-C(7)
1.392(12)
C(20)-H(20)
0.9300
C(7)-C(8)
1.380(13)
C(21)-N(5)
1.340(10)
C(7)-H(7)
0.9300
C(21)-C(22)
1.375(12)
C(8)-C(9)
1.390(13)
C(21)-H(21)
0.9300
C(8)-H(8)
0.9300
C(22)-C(23)
1.356(14)
C(9)-C(10)
1.363(12)
C(22)-H(22)
0.9300
C(9)-H(9)
0.9300
C(23)-C(24)
1.367(14)
C(10)-N(2)
1.362(10)
C(23)-H(23)
0.9300
C(10)-H(10)
0.9300
C(24)-C(25)
1.389(13)
C(11)-N(3)
1.353(10)
C(24)-H(24)
0.9300
C(11)-C(12)
1.376(12)
C(25)-N(5)
1.365(11)
C(11)-H(11)
0.9300
C(25)-C(26)
1.453(13)
C(12)-C(13)
1.354(13)
C(26)-N(6)
1.369(10)
C(12)-H(12)
0.9300
C(26)-C(27)
1.377(12)
C(13)-C(14)
1.375(13)
C(27)-C(28)
1.384(13)
C(13)-H(13)
0.9300
C(27)-H(27)
0.9300
C(14)-C(15)
1.397(12)
C(28)-C(29)
1.371(13)
260
APPENDIX B (continued)
C(28)-H(28)
C(29)-C(30)
C(29)-H(29)
C(30)-N(6)
C(30)-C(31)
C(31)-C(32)
C(31)-H(31A)
C(31)-H(31B)
C(32)-C(33)
C(32)-H(32A)
C(32)-H(32B)
C(33)-N(7)
C(33)-C(34)
C(34)-C(35)
C(34)-H(34)
C(35)-C(36)
C(35)-H(35)
C(36)-C(37)
C(36)-H(36)
C(37)-N(7)
C(37)-C(38)
C(38)-N(8)
C(38)-C(39)
C(39)-C(40)
C(39)-H(39)
C(40)-C(41)
C(40)-H(40)
C(41)-C(42)
C(41)-H(41)
C(42)-N(8)
C(42)-H(42)
C(43)-N(9)
C(43)-C(44)
C(43)-H(43)
C(44)-C(45)
C(44)-H(44)
C(45)-C(46)
C(45)-H(45)
C(46)-C(47)
C(46)-H(46)
C(47)-N(9)
C(47)-C(48)
C(48)-N(10)
0.9300
1.398(12)
0.9300
1.352(10)
1.510(12)
1.522(11)
0.9700
0.9700
1.504(12)
0.9700
0.9700
1.343(11)
1.401(12)
1.357(13)
0.9300
1.375(13)
0.9300
1.399(12)
0.9300
1.363(10)
1.457(12)
1.345(11)
1.356(12)
1.391(13)
0.9300
1.355(13)
0.9300
1.368(12)
0.9300
1.357(11)
0.9300
1.348(10)
1.362(11)
0.9300
1.363(13)
0.9300
1.381(13)
0.9300
1.393(12)
0.9300
1.350(10)
1.487(12)
1.358(11)
C(48)-C(49)
C(49)-C(50)
C(49)-H(49)
C(50)-C(51)
C(50)-H(50)
C(51)-C(52)
C(51)-H(51)
C(52)-N(10)
C(52)-H(52)
C(53)-N(11)
C(53)-C(54)
C(53)-H(53)
C(54)-C(55)
C(54)-H(54)
C(55)-C(56)
C(55)-H(55)
C(56)-C(57)
C(56)-H(56)
C(57)-N(11)
C(57)-C(58)
C(58)-N(12)
C(58)-C(59)
C(59)-C(60)
C(59)-H(59)
C(60)-C(61)
C(60)-H(60)
C(61)-C(62)
C(61)-H(61)
C(62)-N(12)
C(62)-H(62)
C(63)-N(13)
C(63)-C(64)
C(63)-H(63)
C(64)-C(65)
C(64)-H(64)
C(65)-C(66)
C(65)-H(65)
C(66)-C(67)
C(66)-H(66)
C(67)-N(13)
C(67)-C(68)
C(68)-C(69)
C(68)-N(14)
261
1.402(12)
1.379(13)
0.9300
1.375(14)
0.9300
1.384(12)
0.9300
1.360(11)
0.9300
1.327(10)
1.382(12)
0.9300
1.371(12)
0.9300
1.401(12)
0.9300
1.379(12)
0.9300
1.373(10)
1.472(12)
1.351(11)
1.383(12)
1.391(13)
0.9300
1.350(13)
0.9300
1.367(12)
0.9300
1.335(10)
0.9300
1.341(11)
1.371(12)
0.9300
1.376(13)
0.9300
1.384(13)
0.9300
1.393(12)
0.9300
1.372(11)
1.434(12)
1.372(12)
1.383(11)
APPENDIX B (continued)
C(69)-C(70)
C(69)-H(69)
C(70)-C(71)
C(70)-H(70)
C(71)-C(72)
C(71)-H(71)
C(72)-N(14)
C(72)-H(72)
C(73)-N(15)
C(73)-C(74)
C(73)-H(73)
C(74)-C(75)
C(74)-H(74)
C(75)-C(76)
C(75)-H(75)
C(76)-C(77)
C(76)-H(76)
C(77)-N(15)
C(77)-C(78)
C(78)-N(16)
C(78)-C(79)
C(79)-C(80)
C(79)-H(79)
C(80)-C(81)
C(80)-H(80)
C(81)-C(82)
C(81)-H(81)
C(82)-N(16)
C(82)-H(82)
C(83)-N(17)
C(83)-C(84)
C(83)-H(83)
C(84)-C(85)
C(84)-H(84)
C(85)-C(86)
C(85)-H(85)
C(86)-C(87)
C(86)-H(86)
C(87)-N(17)
C(87)-C(88)
C(88)-N(18)
C(88)-C(89)
C(89)-C(90)
1.357(13)
0.9300
1.388(13)
0.9300
1.376(12)
0.9300
1.330(11)
0.9300
1.340(10)
1.393(12)
0.9300
1.362(12)
0.9300
1.361(12)
0.9300
1.381(12)
0.9300
1.358(11)
1.474(12)
1.348(11)
1.393(12)
1.364(13)
0.9300
1.373(13)
0.9300
1.374(12)
0.9300
1.351(11)
0.9300
1.337(11)
1.393(12)
0.9300
1.378(13)
0.9300
1.367(13)
0.9300
1.374(13)
0.9300
1.355(11)
1.464(13)
1.373(11)
1.374(12)
1.367(13)
C(89)-H(89)
C(90)-C(91)
C(90)-H(90)
C(91)-C(92)
C(91)-H(91)
C(92)-N(18)
C(92)-C(93)
C(93)-C(94)
C(93)-H(93A)
C(93)-H(93B)
C(94)-C(95)
C(94)-H(94A)
C(94)-H(94B)
C(95)-N(19)
C(95)-C(96)
C(96)-C(97)
C(96)-H(96)
C(97)-C(98)
C(97)-H(97)
C(98)-C(99)
C(98)-H(98)
C(99)-N(19)
C(99)-C(100)
C(100)-N(20)
C(100)-C(101)
C(101)-C(102)
C(101)-H(101)
C(102)-C(103)
C(102)-H(102)
C(103)-C(104)
C(103)-H(103)
C(104)-N(20)
C(104)-H(104)
C(105)-N(21)
C(105)-C(106)
C(105)-H(105)
C(106)-C(107)
C(106)-H(106)
C(107)-C(108)
C(107)-H(107)
C(108)-C(109)
C(108)-H(108)
C(109)-N(21)
262
0.9300
1.365(13)
0.9300
1.388(12)
0.9300
1.356(10)
1.493(11)
1.524(11)
0.9700
0.9700
1.489(12)
0.9700
0.9700
1.360(11)
1.386(12)
1.365(13)
0.9300
1.366(13)
0.9300
1.393(13)
0.9300
1.368(11)
1.449(13)
1.342(12)
1.398(13)
1.387(14)
0.9300
1.364(14)
0.9300
1.380(12)
0.9300
1.344(11)
0.9300
1.305(11)
1.373(12)
0.9300
1.351(12)
0.9300
1.392(14)
0.9300
1.383(12)
0.9300
1.371(11)
APPENDIX B (continued)
C(109)-C(110)
C(110)-N(22)
C(110)-C(111)
C(111)-C(112)
C(111)-H(111)
C(112)-C(113)
C(112)-H(112)
C(113)-C(114)
C(113)-H(113)
C(114)-N(22)
C(114)-H(114)
C(115)-N(23)
C(115)-C(116)
C(115)-H(115)
C(116)-C(117)
C(116)-H(116)
C(117)-C(118)
C(117)-H(117)
C(118)-C(119)
C(118)-H(118)
C(119)-N(23)
C(119)-C(120)
C(120)-N(24)
C(120)-C(121)
C(121)-C(122)
C(121)-H(121)
C(122)-C(123)
C(122)-H(122)
C(123)-C(124)
C(123)-H(123)
C(124)-N(24)
C(124)-H(124)
F(1)-P(1)
F(2)-P(1)
F(3)-P(1)
F(4)-P(1)
F(5)-P(1)
F(6)-P(1)
F(7)-P(2)
F(8)-P(2)
F(9)-P(2)
F(10)-P(2)
F(11)-P(2)
1.463(13)
1.367(11)
1.395(12)
1.362(13)
0.9300
1.374(13)
0.9300
1.379(12)
0.9300
1.347(11)
0.9300
1.333(10)
1.391(12)
0.9300
1.324(14)
0.9300
1.386(14)
0.9300
1.388(13)
0.9300
1.356(11)
1.450(12)
1.362(11)
1.399(12)
1.382(13)
0.9300
1.371(13)
0.9300
1.379(12)
0.9300
1.346(11)
0.9300
1.602(6)
1.600(6)
1.594(6)
1.591(6)
1.592(6)
1.589(6)
1.588(7)
1.604(6)
1.595(8)
1.584(7)
1.604(6)
F(12)-P(2)
F(13)-P(3)
F(14)-P(3)
F(15)-P(3)
F(16)-P(3)
F(17)-P(3)
F(18)-P(3)
F(19)-P(4)
F(20)-P(4)
F(21)-P(4)
F(22)-P(4)
F(23)-P(4)
F(24)-P(4)
F(25)-P(5)
F(26)-P(5)
F(27)-P(5)
F(28)-P(5)
F(29)-P(5)
F(30)-P(5)
F(31)-P(6)
F(32)-P(6)
F(33)-P(6)
F(34)-P(6)
F(35)-P(6)
F(36)-P(6)
F(37)-P(7)
F(38)-P(7)
F(39)-P(7)
F(40)-P(7)
F(41)-P(7)
F(42)-P(7)
F(43)-P(8)
F(44)-P(8)
F(45)-P(8)
F(46)-P(8)
F(47)-P(8)
F(48)-P(8)
N(1)-Ru(1)
N(2)-Ru(1)
N(3)-Ru(1)
N(4)-Ru(1)
N(5)-Ru(1)
N(6)-Ru(1)
263
1.606(7)
1.600(6)
1.585(6)
1.603(6)
1.589(6)
1.588(6)
1.579(6)
1.577(7)
1.594(6)
1.589(6)
1.580(7)
1.608(6)
1.568(7)
1.589(7)
1.566(6)
1.560(7)
1.568(6)
1.553(7)
1.593(7)
1.582(6)
1.598(7)
1.584(6)
1.602(7)
1.596(6)
1.606(6)
1.586(7)
1.566(8)
1.607(7)
1.578(6)
1.537(8)
1.552(7)
1.615(6)
1.599(6)
1.597(6)
1.597(6)
1.595(6)
1.597(6)
2.082(7)
2.060(7)
2.044(7)
2.058(7)
2.048(7)
2.124(7)
APPENDIX B (continued)
N(7)-Ru(2)
N(8)-Ru(2)
N(9)-Ru(2)
N(10)-Ru(2)
N(11)-Ru(2)
N(12)-Ru(2)
N(13)-Ru(3)
N(14)-Ru(3)
N(15)-Ru(3)
N(16)-Ru(3)
2.149(7)
2.054(7)
2.042(7)
2.046(8)
2.066(7)
2.043(7)
2.058(7)
2.053(7)
2.074(7)
2.054(7)
N(17)-Ru(3)
N(18)-Ru(3)
N(19)-Ru(4)
N(20)-Ru(4)
N(21)-Ru(4)
N(22)-Ru(4)
N(23)-Ru(4)
N(24)-Ru(4)
2.058(7)
2.142(7)
2.144(7)
2.049(7)
2.056(7)
2.075(7)
2.054(8)
2.053(8)
Bond angles [deg]
________________________________________________________________________________
N(1)-C(1)-C(2)
124.1(9)
C(9)-C(10)-H(10)
118.5
N(1)-C(1)-H(1)
117.9
N(3)-C(11)-C(12)
122.3(9)
C(2)-C(1)-H(1)
117.9
N(3)-C(11)-H(11)
118.8
C(1)-C(2)-C(3)
118.4(9)
C(12)-C(11)-H(11)
118.8
C(1)-C(2)-H(2)
120.8
C(13)-C(12)-C(11)
119.9(10)
C(3)-C(2)-H(2)
120.8
C(13)-C(12)-H(12)
120.0
C(2)-C(3)-C(4)
119.5(10)
C(11)-C(12)-H(12)
120.0
C(2)-C(3)-H(3)
120.2
C(12)-C(13)-C(14)
119.5(10)
C(4)-C(3)-H(3)
120.3
C(12)-C(13)-H(13)
120.3
C(5)-C(4)-C(3)
120.3(10)
C(14)-C(13)-H(13)
120.3
C(5)-C(4)-H(4)
119.8
C(13)-C(14)-C(15)
118.9(10)
C(3)-C(4)-H(4)
119.8
C(13)-C(14)-H(14)
120.6
C(4)-C(5)-N(1)
119.7(9)
C(15)-C(14)-H(14)
120.6
C(4)-C(5)-C(6)
124.6(9)
N(3)-C(15)-C(14)
121.8(9)
N(1)-C(5)-C(6)
115.7(8)
N(3)-C(15)-C(16)
116.5(8)
N(2)-C(6)-C(7)
121.4(9)
C(14)-C(15)-C(16)
121.7(9)
N(2)-C(6)-C(5)
115.1(8)
C(17)-C(16)-N(4)
121.0(9)
C(7)-C(6)-C(5)
123.4(9)
C(17)-C(16)-C(15)
126.3(9)
C(8)-C(7)-C(6)
118.4(9)
N(4)-C(16)-C(15)
112.7(8)
C(8)-C(7)-H(7)
120.8
C(16)-C(17)-C(18)
120.5(10)
C(6)-C(7)-H(7)
120.8
C(16)-C(17)-H(17)
119.7
C(7)-C(8)-C(9)
120.8(9)
C(18)-C(17)-H(17)
119.7
C(7)-C(8)-H(8)
119.6
C(19)-C(18)-C(17)
119.1(10)
C(9)-C(8)-H(8)
119.6
C(19)-C(18)-H(18)
120.4
C(10)-C(9)-C(8)
117.6(9)
C(17)-C(18)-H(18)
120.4
C(10)-C(9)-H(9)
121.2
C(18)-C(19)-C(20)
119.7(9)
C(8)-C(9)-H(9)
121.2
C(18)-C(19)-H(19)
120.1
N(2)-C(10)-C(9)
123.0(9)
C(20)-C(19)-H(19)
120.1
N(2)-C(10)-H(10)
118.5
N(4)-C(20)-C(19)
121.0(9)
264
APPENDIX B (continued)
N(4)-C(20)-H(20)
C(19)-C(20)-H(20)
N(5)-C(21)-C(22)
N(5)-C(21)-H(21)
C(22)-C(21)-H(21)
C(23)-C(22)-C(21)
C(23)-C(22)-H(22)
C(21)-C(22)-H(22)
C(22)-C(23)-C(24)
C(22)-C(23)-H(23)
C(24)-C(23)-H(23)
C(23)-C(24)-C(25)
C(23)-C(24)-H(24)
C(25)-C(24)-H(24)
N(5)-C(25)-C(24)
N(5)-C(25)-C(26)
C(24)-C(25)-C(26)
N(6)-C(26)-C(27)
N(6)-C(26)-C(25)
C(27)-C(26)-C(25)
C(26)-C(27)-C(28)
C(26)-C(27)-H(27)
C(28)-C(27)-H(27)
C(29)-C(28)-C(27)
C(29)-C(28)-H(28)
C(27)-C(28)-H(28)
C(28)-C(29)-C(30)
C(28)-C(29)-H(29)
C(30)-C(29)-H(29)
N(6)-C(30)-C(29)
N(6)-C(30)-C(31)
C(29)-C(30)-C(31)
C(30)-C(31)-C(32)
C(30)-C(31)-H(31A)
C(32)-C(31)-H(31A)
C(30)-C(31)-H(31B)
C(32)-C(31)-H(31B)
H(31A)-C(31)-H(31B)
C(33)-C(32)-C(31)
C(33)-C(32)-H(32A)
C(31)-C(32)-H(32A)
C(33)-C(32)-H(32B)
C(31)-C(32)-H(32B)
119.5
119.5
122.2(9)
118.9
118.9
120.5(10)
119.7
119.7
117.8(10)
121.1
121.1
121.0(10)
119.5
119.5
120.2(9)
114.9(8)
124.9(9)
122.6(9)
116.2(8)
121.1(9)
120.5(9)
119.7
119.7
117.1(9)
121.4
121.4
120.8(9)
119.6
119.6
122.0(9)
118.0(8)
119.9(8)
114.6(7)
108.6
108.6
108.6
108.6
107.6
113.4(7)
108.9
108.9
108.9
108.9
H(32A)-C(32)-H(32B)
N(7)-C(33)-C(34)
N(7)-C(33)-C(32)
C(34)-C(33)-C(32)
C(35)-C(34)-C(33)
C(35)-C(34)-H(34)
C(33)-C(34)-H(34)
C(34)-C(35)-C(36)
C(34)-C(35)-H(35)
C(36)-C(35)-H(35)
C(35)-C(36)-C(37)
C(35)-C(36)-H(36)
C(37)-C(36)-H(36)
N(7)-C(37)-C(36)
N(7)-C(37)-C(38)
C(36)-C(37)-C(38)
N(8)-C(38)-C(39)
N(8)-C(38)-C(37)
C(39)-C(38)-C(37)
C(38)-C(39)-C(40)
C(38)-C(39)-H(39)
C(40)-C(39)-H(39)
C(41)-C(40)-C(39)
C(41)-C(40)-H(40)
C(39)-C(40)-H(40)
C(40)-C(41)-C(42)
C(40)-C(41)-H(41)
C(42)-C(41)-H(41)
N(8)-C(42)-C(41)
N(8)-C(42)-H(42)
C(41)-C(42)-H(42)
N(9)-C(43)-C(44)
N(9)-C(43)-H(43)
C(44)-C(43)-H(43)
C(43)-C(44)-C(45)
C(43)-C(44)-H(44)
C(45)-C(44)-H(44)
C(44)-C(45)-C(46)
C(44)-C(45)-H(45)
C(46)-C(45)-H(45)
C(45)-C(46)-C(47)
C(45)-C(46)-H(46)
C(47)-C(46)-H(46)
265
107.7
121.3(9)
119.3(8)
119.4(9)
119.8(10)
120.1
120.1
119.5(9)
120.3
120.3
119.4(9)
120.3
120.3
120.8(9)
118.0(8)
121.0(9)
121.6(9)
114.1(8)
124.3(9)
120.5(9)
119.8
119.8
117.2(9)
121.4
121.4
120.9(10)
119.5
119.5
121.3(9)
119.4
119.4
123.3(9)
118.4
118.4
119.4(9)
120.3
120.3
119.7(10)
120.2
120.2
117.8(9)
121.1
121.1
APPENDIX B (continued)
N(9)-C(47)-C(46)
N(9)-C(47)-C(48)
C(46)-C(47)-C(48)
N(10)-C(48)-C(49)
N(10)-C(48)-C(47)
C(49)-C(48)-C(47)
C(50)-C(49)-C(48)
C(50)-C(49)-H(49)
C(48)-C(49)-H(49)
C(51)-C(50)-C(49)
C(51)-C(50)-H(50)
C(49)-C(50)-H(50)
C(50)-C(51)-C(52)
C(50)-C(51)-H(51)
C(52)-C(51)-H(51)
N(10)-C(52)-C(51)
N(10)-C(52)-H(52)
C(51)-C(52)-H(52)
N(11)-C(53)-C(54)
N(11)-C(53)-H(53)
C(54)-C(53)-H(53)
C(55)-C(54)-C(53)
C(55)-C(54)-H(54)
C(53)-C(54)-H(54)
C(54)-C(55)-C(56)
C(54)-C(55)-H(55)
C(56)-C(55)-H(55)
C(57)-C(56)-C(55)
C(57)-C(56)-H(56)
C(55)-C(56)-H(56)
N(11)-C(57)-C(56)
N(11)-C(57)-C(58)
C(56)-C(57)-C(58)
N(12)-C(58)-C(59)
N(12)-C(58)-C(57)
C(59)-C(58)-C(57)
C(58)-C(59)-C(60)
C(58)-C(59)-H(59)
C(60)-C(59)-H(59)
C(61)-C(60)-C(59)
C(61)-C(60)-H(60)
C(59)-C(60)-H(60)
C(60)-C(61)-C(62)
122.8(8)
114.8(8)
122.4(9)
122.3(9)
113.4(8)
124.3(9)
117.3(10)
121.4
121.4
121.8(10)
119.1
119.1
117.8(10)
121.1
121.1
122.7(10)
118.7
118.7
124.3(9)
117.8
117.8
118.6(9)
120.7
120.7
118.5(9)
120.7
120.7
119.7(9)
120.2
120.2
121.5(8)
114.9(8)
123.6(8)
121.4(8)
115.1(8)
123.4(9)
118.4(9)
120.8
120.8
119.6(10)
120.2
120.2
119.5(10)
C(60)-C(61)-H(61)
C(62)-C(61)-H(61)
N(12)-C(62)-C(61)
N(12)-C(62)-H(62)
C(61)-C(62)-H(62)
N(13)-C(63)-C(64)
N(13)-C(63)-H(63)
C(64)-C(63)-H(63)
C(63)-C(64)-C(65)
C(63)-C(64)-H(64)
C(65)-C(64)-H(64)
C(64)-C(65)-C(66)
C(64)-C(65)-H(65)
C(66)-C(65)-H(65)
C(67)-C(66)-C(65)
C(67)-C(66)-H(66)
C(65)-C(66)-H(66)
N(13)-C(67)-C(66)
N(13)-C(67)-C(68)
C(66)-C(67)-C(68)
C(69)-C(68)-N(14)
C(69)-C(68)-C(67)
N(14)-C(68)-C(67)
C(70)-C(69)-C(68)
C(70)-C(69)-H(69)
C(68)-C(69)-H(69)
C(69)-C(70)-C(71)
C(69)-C(70)-H(70)
C(71)-C(70)-H(70)
C(72)-C(71)-C(70)
C(72)-C(71)-H(71)
C(70)-C(71)-H(71)
N(14)-C(72)-C(71)
N(14)-C(72)-H(72)
C(71)-C(72)-H(72)
N(15)-C(73)-C(74)
N(15)-C(73)-H(73)
C(74)-C(73)-H(73)
C(75)-C(74)-C(73)
C(75)-C(74)-H(74)
C(73)-C(74)-H(74)
C(76)-C(75)-C(74)
C(76)-C(75)-H(75)
266
120.3
120.3
122.6(9)
118.7
118.7
122.7(9)
118.6
118.6
119.3(10)
120.4
120.4
118.8(10)
120.6
120.6
120.3(10)
119.8
119.8
119.6(9)
116.5(8)
123.9(9)
120.5(9)
124.7(9)
114.7(8)
120.8(9)
119.6
119.6
118.8(10)
120.6
120.6
118.8(9)
120.6
120.6
122.9(9)
118.5
118.5
122.0(9)
119.0
119.0
118.5(9)
120.8
120.8
120.6(9)
119.7
APPENDIX B (continued)
C(74)-C(75)-H(75)
C(75)-C(76)-C(77)
C(75)-C(76)-H(76)
C(77)-C(76)-H(76)
N(15)-C(77)-C(76)
N(15)-C(77)-C(78)
C(76)-C(77)-C(78)
N(16)-C(78)-C(79)
N(16)-C(78)-C(77)
C(79)-C(78)-C(77)
C(80)-C(79)-C(78)
C(80)-C(79)-H(79)
C(78)-C(79)-H(79)
C(79)-C(80)-C(81)
C(79)-C(80)-H(80)
C(81)-C(80)-H(80)
C(80)-C(81)-C(82)
C(80)-C(81)-H(81)
C(82)-C(81)-H(81)
N(16)-C(82)-C(81)
N(16)-C(82)-H(82)
C(81)-C(82)-H(82)
N(17)-C(83)-C(84)
N(17)-C(83)-H(83)
C(84)-C(83)-H(83)
C(85)-C(84)-C(83)
C(85)-C(84)-H(84)
C(83)-C(84)-H(84)
C(86)-C(85)-C(84)
C(86)-C(85)-H(85)
C(84)-C(85)-H(85)
C(85)-C(86)-C(87)
C(85)-C(86)-H(86)
C(87)-C(86)-H(86)
N(17)-C(87)-C(86)
N(17)-C(87)-C(88)
C(86)-C(87)-C(88)
N(18)-C(88)-C(89)
N(18)-C(88)-C(87)
C(89)-C(88)-C(87)
C(90)-C(89)-C(88)
C(90)-C(89)-H(89)
C(88)-C(89)-H(89)
119.7
118.9(9)
120.5
120.5
121.7(8)
115.4(8)
122.9(9)
120.0(8)
114.8(8)
125.1(8)
120.1(9)
119.9
119.9
119.3(10)
120.3
120.3
119.4(10)
120.3
120.3
121.4(9)
119.3
119.3
123.2(9)
118.4
118.4
118.5(10)
120.8
120.8
117.6(10)
121.2
121.2
122.3(10)
118.8
118.8
120.0(9)
115.2(8)
124.8(9)
122.8(9)
115.6(8)
121.6(9)
119.0(9)
120.5
120.5
C(91)-C(90)-C(89)
C(91)-C(90)-H(90)
C(89)-C(90)-H(90)
C(90)-C(91)-C(92)
C(90)-C(91)-H(91)
C(92)-C(91)-H(91)
N(18)-C(92)-C(91)
N(18)-C(92)-C(93)
C(91)-C(92)-C(93)
C(92)-C(93)-C(94)
C(92)-C(93)-H(93A)
C(94)-C(93)-H(93A)
C(92)-C(93)-H(93B)
C(94)-C(93)-H(93B)
H(93A)-C(93)-H(93B)
C(95)-C(94)-C(93)
C(95)-C(94)-H(94A)
C(93)-C(94)-H(94A)
C(95)-C(94)-H(94B)
C(93)-C(94)-H(94B)
H(94A)-C(94)-H(94B)
N(19)-C(95)-C(96)
N(19)-C(95)-C(94)
C(96)-C(95)-C(94)
C(97)-C(96)-C(95)
C(97)-C(96)-H(96)
C(95)-C(96)-H(96)
C(98)-C(97)-C(96)
C(98)-C(97)-H(97)
C(96)-C(97)-H(97)
C(97)-C(98)-C(99)
C(97)-C(98)-H(98)
C(99)-C(98)-H(98)
N(19)-C(99)-C(98)
N(19)-C(99)-C(100)
C(98)-C(99)-C(100)
N(20)-C(100)-C(101)
N(20)-C(100)-C(99)
C(101)-C(100)-C(99)
C(102)-C(101)-C(100)
C(102)-C(101)-H(101)
C(100)-C(101)-H(101)
C(103)-C(102)-C(101)
267
119.2(9)
120.4
120.4
120.4(9)
119.8
119.8
121.1(8)
119.0(8)
119.8(8)
114.8(7)
108.6
108.6
108.6
108.6
107.5
113.3(7)
108.9
108.9
108.9
108.9
107.7
121.8(9)
118.3(8)
119.9(9)
119.6(10)
120.2
120.2
119.8(10)
120.1
120.1
119.3(10)
120.4
120.4
121.5(9)
116.1(9)
122.4(9)
121.1(10)
115.9(8)
122.9(10)
120.5(11)
119.8
119.8
117.4(10)
APPENDIX B (continued)
C(103)-C(102)-H(102)
C(101)-C(102)-H(102)
C(102)-C(103)-C(104)
C(102)-C(103)-H(103)
C(104)-C(103)-H(103)
N(20)-C(104)-C(103)
N(20)-C(104)-H(104)
C(103)-C(104)-H(104)
N(21)-C(105)-C(106)
N(21)-C(105)-H(105)
C(106)-C(105)-H(105)
C(107)-C(106)-C(105)
C(107)-C(106)-H(106)
C(105)-C(106)-H(106)
C(106)-C(107)-C(108)
C(106)-C(107)-H(107)
C(108)-C(107)-H(107)
C(109)-C(108)-C(107)
C(109)-C(108)-H(108)
C(107)-C(108)-H(108)
N(21)-C(109)-C(108)
N(21)-C(109)-C(110)
C(108)-C(109)-C(110)
N(22)-C(110)-C(111)
N(22)-C(110)-C(109)
C(111)-C(110)-C(109)
C(112)-C(111)-C(110)
C(112)-C(111)-H(111)
C(110)-C(111)-H(111)
C(111)-C(112)-C(113)
C(111)-C(112)-H(112)
C(113)-C(112)-H(112)
C(112)-C(113)-C(114)
C(112)-C(113)-H(113)
C(114)-C(113)-H(113)
N(22)-C(114)-C(113)
N(22)-C(114)-H(114)
C(113)-C(114)-H(114)
N(23)-C(115)-C(116)
N(23)-C(115)-H(115)
C(116)-C(115)-H(115)
C(117)-C(116)-C(115)
C(117)-C(116)-H(116)
121.3
121.3
119.7(10)
120.2
120.2
123.5(9)
118.2
118.2
124.4(9)
117.8
117.8
118.6(10)
120.7
120.7
118.8(10)
120.6
120.6
120.0(9)
120.0
120.0
119.7(9)
115.1(9)
125.0(9)
119.3(9)
116.1(8)
124.6(10)
121.0(10)
119.5
119.5
119.6(9)
120.2
120.2
118.2(10)
120.9
120.9
123.1(10)
118.4
118.4
121.1(9)
119.4
119.4
120.6(10)
119.7
C(115)-C(116)-H(116)
C(116)-C(117)-C(118)
C(116)-C(117)-H(117)
C(118)-C(117)-H(117)
C(117)-C(118)-C(119)
C(117)-C(118)-H(118)
C(119)-C(118)-H(118)
N(23)-C(119)-C(118)
N(23)-C(119)-C(120)
C(118)-C(119)-C(120)
N(24)-C(120)-C(121)
N(24)-C(120)-C(119)
C(121)-C(120)-C(119)
C(122)-C(121)-C(120)
C(122)-C(121)-H(121)
C(120)-C(121)-H(121)
C(123)-C(122)-C(121)
C(123)-C(122)-H(122)
C(121)-C(122)-H(122)
C(122)-C(123)-C(124)
C(122)-C(123)-H(123)
C(124)-C(123)-H(123)
N(24)-C(124)-C(123)
N(24)-C(124)-H(124)
C(123)-C(124)-H(124)
C(1)-N(1)-C(5)
C(1)-N(1)-Ru(1)
C(5)-N(1)-Ru(1)
C(6)-N(2)-C(10)
C(6)-N(2)-Ru(1)
C(10)-N(2)-Ru(1)
C(15)-N(3)-C(11)
C(15)-N(3)-Ru(1)
C(11)-N(3)-Ru(1)
C(20)-N(4)-C(16)
C(20)-N(4)-Ru(1)
C(16)-N(4)-Ru(1)
C(21)-N(5)-C(25)
C(21)-N(5)-Ru(1)
C(25)-N(5)-Ru(1)
C(30)-N(6)-C(26)
C(30)-N(6)-Ru(1)
C(26)-N(6)-Ru(1)
268
119.7
119.1(10)
120.5
120.5
119.8(10)
120.1
120.1
119.9(9)
115.6(9)
124.4(9)
120.9(9)
115.0(8)
124.0(9)
119.3(9)
120.4
120.4
119.5(9)
120.2
120.2
119.1(10)
120.4
120.4
122.7(9)
118.6
118.6
117.9(8)
127.8(7)
113.4(6)
118.7(8)
115.8(6)
125.0(6)
117.6(8)
114.8(6)
127.4(6)
118.6(8)
125.3(6)
116.0(6)
118.1(8)
125.4(6)
116.5(6)
116.4(8)
130.6(6)
112.8(6)
APPENDIX B (continued)
C(33)-N(7)-C(37)
C(33)-N(7)-Ru(2)
C(37)-N(7)-Ru(2)
C(38)-N(8)-C(42)
C(38)-N(8)-Ru(2)
C(42)-N(8)-Ru(2)
C(43)-N(9)-C(47)
C(43)-N(9)-Ru(2)
C(47)-N(9)-Ru(2)
C(48)-N(10)-C(52)
C(48)-N(10)-Ru(2)
C(52)-N(10)-Ru(2)
C(53)-N(11)-C(57)
C(53)-N(11)-Ru(2)
C(57)-N(11)-Ru(2)
C(62)-N(12)-C(58)
C(62)-N(12)-Ru(2)
C(58)-N(12)-Ru(2)
C(63)-N(13)-C(67)
C(63)-N(13)-Ru(3)
C(67)-N(13)-Ru(3)
C(72)-N(14)-C(68)
C(72)-N(14)-Ru(3)
C(68)-N(14)-Ru(3)
C(73)-N(15)-C(77)
C(73)-N(15)-Ru(3)
C(77)-N(15)-Ru(3)
C(78)-N(16)-C(82)
C(78)-N(16)-Ru(3)
C(82)-N(16)-Ru(3)
C(83)-N(17)-C(87)
C(83)-N(17)-Ru(3)
C(87)-N(17)-Ru(3)
C(92)-N(18)-C(88)
C(92)-N(18)-Ru(3)
C(88)-N(18)-Ru(3)
C(95)-N(19)-C(99)
C(95)-N(19)-Ru(4)
C(99)-N(19)-Ru(4)
C(104)-N(20)-C(100)
C(104)-N(20)-Ru(4)
C(100)-N(20)-Ru(4)
C(105)-N(21)-C(109)
118.8(8)
129.3(6)
111.1(6)
118.0(8)
117.3(6)
124.6(6)
116.9(8)
126.9(6)
116.3(6)
118.1(8)
116.5(6)
125.1(7)
117.3(8)
127.5(6)
114.1(6)
118.5(8)
125.7(6)
115.8(6)
119.2(8)
126.5(7)
114.3(6)
118.0(8)
127.0(7)
115.0(6)
118.3(8)
126.4(6)
114.4(6)
119.7(8)
115.9(6)
124.4(7)
118.2(8)
124.9(6)
116.9(6)
117.1(8)
129.2(6)
113.2(6)
117.5(8)
130.4(6)
111.8(6)
117.3(8)
126.4(6)
116.3(6)
118.4(8)
C(105)-N(21)-Ru(4)
C(109)-N(21)-Ru(4)
C(114)-N(22)-C(110)
C(114)-N(22)-Ru(4)
C(110)-N(22)-Ru(4)
C(115)-N(23)-C(119)
C(115)-N(23)-Ru(4)
C(119)-N(23)-Ru(4)
C(124)-N(24)-C(120)
C(124)-N(24)-Ru(4)
C(120)-N(24)-Ru(4)
F(6)-P(1)-F(4)
F(6)-P(1)-F(5)
F(4)-P(1)-F(5)
F(6)-P(1)-F(3)
F(4)-P(1)-F(3)
F(5)-P(1)-F(3)
F(6)-P(1)-F(2)
F(4)-P(1)-F(2)
F(5)-P(1)-F(2)
F(3)-P(1)-F(2)
F(6)-P(1)-F(1)
F(4)-P(1)-F(1)
F(5)-P(1)-F(1)
F(3)-P(1)-F(1)
F(2)-P(1)-F(1)
F(10)-P(2)-F(7)
F(10)-P(2)-F(9)
F(7)-P(2)-F(9)
F(10)-P(2)-F(8)
F(7)-P(2)-F(8)
F(9)-P(2)-F(8)
F(10)-P(2)-F(12)
F(7)-P(2)-F(12)
F(9)-P(2)-F(12)
F(8)-P(2)-F(12)
F(10)-P(2)-F(11)
F(7)-P(2)-F(11)
F(9)-P(2)-F(11)
F(8)-P(2)-F(11)
F(12)-P(2)-F(11)
F(18)-P(3)-F(14)
F(18)-P(3)-F(17)
269
126.4(7)
114.8(6)
118.8(8)
126.9(7)
113.8(6)
119.5(8)
125.9(7)
114.5(6)
118.5(8)
126.7(7)
114.8(6)
90.0(3)
90.3(4)
90.8(4)
179.2(4)
89.4(3)
89.2(3)
89.3(4)
90.0(4)
179.1(4)
91.2(4)
90.9(4)
178.6(4)
90.3(3)
89.8(3)
88.9(3)
90.8(4)
90.3(4)
90.9(5)
179.8(4)
89.1(4)
89.7(4)
91.3(4)
89.7(4)
178.3(4)
88.7(4)
90.4(4)
178.5(4)
90.1(4)
89.8(4)
89.3(3)
91.3(4)
89.3(3)
APPENDIX B (continued)
F(14)-P(3)-F(17)
F(18)-P(3)-F(16)
F(14)-P(3)-F(16)
F(17)-P(3)-F(16)
F(18)-P(3)-F(15)
F(14)-P(3)-F(15)
F(17)-P(3)-F(15)
F(16)-P(3)-F(15)
F(18)-P(3)-F(13)
F(14)-P(3)-F(13)
F(17)-P(3)-F(13)
F(16)-P(3)-F(13)
F(15)-P(3)-F(13)
F(24)-P(4)-F(19)
F(24)-P(4)-F(22)
F(19)-P(4)-F(22)
F(24)-P(4)-F(21)
F(19)-P(4)-F(21)
F(22)-P(4)-F(21)
F(24)-P(4)-F(20)
F(19)-P(4)-F(20)
F(22)-P(4)-F(20)
F(21)-P(4)-F(20)
F(24)-P(4)-F(23)
F(19)-P(4)-F(23)
F(22)-P(4)-F(23)
F(21)-P(4)-F(23)
F(20)-P(4)-F(23)
F(29)-P(5)-F(27)
F(29)-P(5)-F(26)
F(27)-P(5)-F(26)
F(29)-P(5)-F(28)
F(27)-P(5)-F(28)
F(26)-P(5)-F(28)
F(29)-P(5)-F(25)
F(27)-P(5)-F(25)
F(26)-P(5)-F(25)
F(28)-P(5)-F(25)
F(29)-P(5)-F(30)
F(27)-P(5)-F(30)
F(26)-P(5)-F(30)
F(28)-P(5)-F(30)
F(25)-P(5)-F(30)
179.1(4)
90.2(3)
90.9(4)
89.8(3)
179.4(4)
89.3(4)
90.1(4)
89.8(3)
90.1(4)
89.4(4)
89.9(3)
179.5(5)
89.8(4)
90.3(5)
178.4(5)
89.4(4)
89.6(4)
178.7(4)
90.6(4)
91.7(4)
90.5(4)
89.9(4)
90.8(3)
88.7(4)
89.8(4)
89.7(4)
89.0(3)
179.5(4)
92.9(5)
92.6(4)
91.9(4)
177.4(5)
89.1(4)
89.0(4)
88.9(4)
90.7(4)
177.0(5)
89.5(4)
88.1(5)
179.0(4)
87.8(4)
90.0(4)
89.6(4)
F(31)-P(6)-F(33)
F(31)-P(6)-F(35)
F(33)-P(6)-F(35)
F(31)-P(6)-F(32)
F(33)-P(6)-F(32)
F(35)-P(6)-F(32)
F(31)-P(6)-F(34)
F(33)-P(6)-F(34)
F(35)-P(6)-F(34)
F(32)-P(6)-F(34)
F(31)-P(6)-F(36)
F(33)-P(6)-F(36)
F(35)-P(6)-F(36)
F(32)-P(6)-F(36)
F(34)-P(6)-F(36)
F(41)-P(7)-F(42)
F(41)-P(7)-F(38)
F(42)-P(7)-F(38)
F(41)-P(7)-F(40)
F(42)-P(7)-F(40)
F(38)-P(7)-F(40)
F(41)-P(7)-F(37)
F(42)-P(7)-F(37)
F(38)-P(7)-F(37)
F(40)-P(7)-F(37)
F(41)-P(7)-F(39)
F(42)-P(7)-F(39)
F(38)-P(7)-F(39)
F(40)-P(7)-F(39)
F(37)-P(7)-F(39)
F(48)-P(8)-F(47)
F(48)-P(8)-F(46)
F(47)-P(8)-F(46)
F(48)-P(8)-F(45)
F(47)-P(8)-F(45)
F(46)-P(8)-F(45)
F(48)-P(8)-F(44)
F(47)-P(8)-F(44)
F(46)-P(8)-F(44)
F(45)-P(8)-F(44)
F(48)-P(8)-F(43)
F(47)-P(8)-F(43)
F(46)-P(8)-F(43)
270
90.5(4)
179.8(6)
89.6(3)
90.2(4)
90.3(4)
89.6(3)
89.2(4)
90.6(4)
90.9(3)
179.0(4)
89.8(4)
179.6(4)
90.1(4)
90.0(4)
89.1(4)
93.0(6)
91.6(6)
175.3(6)
91.4(5)
91.5(4)
89.1(4)
90.1(5)
87.8(4)
91.4(5)
178.4(4)
178.6(6)
88.3(4)
87.0(5)
88.5(4)
90.0(4)
90.9(3)
89.6(3)
89.9(3)
179.6(4)
89.5(3)
90.4(3)
90.1(3)
90.8(3)
179.2(4)
89.8(3)
89.7(3)
178.9(4)
89.2(3)
APPENDIX B (continued)
F(45)-P(8)-F(43)
F(44)-P(8)-F(43)
N(3)-Ru(1)-N(5)
N(3)-Ru(1)-N(2)
N(5)-Ru(1)-N(2)
N(3)-Ru(1)-N(4)
N(5)-Ru(1)-N(4)
N(2)-Ru(1)-N(4)
N(3)-Ru(1)-N(1)
N(5)-Ru(1)-N(1)
N(2)-Ru(1)-N(1)
N(4)-Ru(1)-N(1)
N(3)-Ru(1)-N(6)
N(5)-Ru(1)-N(6)
N(2)-Ru(1)-N(6)
N(4)-Ru(1)-N(6)
N(1)-Ru(1)-N(6)
N(9)-Ru(2)-N(12)
N(9)-Ru(2)-N(10)
N(12)-Ru(2)-N(10)
N(9)-Ru(2)-N(8)
N(12)-Ru(2)-N(8)
N(10)-Ru(2)-N(8)
N(9)-Ru(2)-N(11)
N(12)-Ru(2)-N(11)
N(10)-Ru(2)-N(11)
N(8)-Ru(2)-N(11)
N(9)-Ru(2)-N(7)
N(12)-Ru(2)-N(7)
N(10)-Ru(2)-N(7)
N(8)-Ru(2)-N(7)
89.9(3)
90.1(3)
95.0(3)
92.9(3)
94.7(3)
79.2(3)
92.1(3)
170.1(3)
81.7(3)
172.9(3)
79.2(3)
93.4(3)
172.5(3)
78.6(3)
91.5(3)
96.9(3)
105.1(3)
172.7(3)
78.7(3)
95.1(3)
88.9(3)
95.5(3)
95.5(3)
95.8(3)
79.4(3)
82.7(3)
174.5(3)
98.7(3)
87.8(3)
173.6(3)
78.4(3)
N(11)-Ru(2)-N(7)
N(14)-Ru(3)-N(16)
N(14)-Ru(3)-N(13)
N(16)-Ru(3)-N(13)
N(14)-Ru(3)-N(17)
N(16)-Ru(3)-N(17)
N(13)-Ru(3)-N(17)
N(14)-Ru(3)-N(15)
N(16)-Ru(3)-N(15)
N(13)-Ru(3)-N(15)
N(17)-Ru(3)-N(15)
N(14)-Ru(3)-N(18)
N(16)-Ru(3)-N(18)
N(13)-Ru(3)-N(18)
N(17)-Ru(3)-N(18)
N(15)-Ru(3)-N(18)
N(20)-Ru(4)-N(24)
N(20)-Ru(4)-N(21)
N(24)-Ru(4)-N(21)
N(20)-Ru(4)-N(23)
N(24)-Ru(4)-N(23)
N(21)-Ru(4)-N(23)
N(20)-Ru(4)-N(22)
N(24)-Ru(4)-N(22)
N(21)-Ru(4)-N(22)
N(23)-Ru(4)-N(22)
N(20)-Ru(4)-N(19)
N(24)-Ru(4)-N(19)
N(21)-Ru(4)-N(19)
N(23)-Ru(4)-N(19)
N(22)-Ru(4)-N(19)
271
103.5(3)
172.7(3)
79.4(3)
95.2(3)
89.5(3)
95.8(3)
94.9(3)
95.4(3)
79.0(3)
82.3(3)
173.8(3)
97.4(3)
88.6(3)
172.3(3)
78.1(3)
105.0(3)
95.0(3)
94.8(3)
93.2(3)
91.6(3)
79.0(3)
170.3(3)
173.8(3)
82.6(3)
79.7(3)
93.6(3)
78.5(3)
172.5(3)
90.9(3)
97.5(3)
104.3(3)
APPENDIX C
CHAPTER 4 SUPPLEMENTARY INFORMATION
Raw kinetic data
Conc. of Anion
0.010 M
0.008 M
0.006 M
0.004 M
0.002 M
Temperature
298
292
289
286
Bromide
1.767
1.719
1.566
1.275
0.862
kobs
SCN
5.222
4.876
4.336
3.520
2.327
Chloride
12.582
12.321
11.001
9.118
6.029
1.767
0.755
0.635
0.269
5.222
2.208
1.737
0.894
12.582
3.889
2.929
1.765
Cartesian Coordinates
Fe(bpz)32+
Number
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
Atom
Fe
C
C
C
C
C
H
H
C
H
C
H
C
H
H
C
C
C
C
X
-0.0023
-0.0133
2.1969
0.4669
-1.4316
2.6519
2.8964
-0.2042
-2.5132
3.7117
-2.9573
-2.3610
-4.0199
-3.1477
-5.0527
2.1664
2.4598
3.3431
1.3261
272
Y
-0.0032
0.0139
0.0148
-0.0173
0.0306
-0.0128
0.0308
-0.0364
0.0822
-0.0223
0.0063
0.1188
0.0548
-0.0274
0.0634
-1.4047
0.8982
-1.6323
-2.4561
Z
0.0002
2.8640
2.0959
4.1915
2.4820
3.4288
1.2713
5.0436
3.3882
3.6605
0.7078
4.4616
1.6314
-0.3563
1.2995
-1.2385
-1.5335
-1.9851
-0.6498
APPENDIX C (continued)
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
C
H
H
C
H
C
H
C
H
H
C
C
C
C
C
H
H
C
H
C
H
C
H
H
N
N
N
N
N
N
N
N
N
N
N
N
3.6323
2.1216
3.7123
1.6098
4.2212
-0.6291
2.4995
-0.3258
-1.5254
-0.9793
-0.8133
0.2780
-1.0301
-1.2488
0.0523
0.8033
-1.5542
-1.8904
0.3949
-1.3632
-2.1060
-2.0050
-1.1630
-2.3096
4.0728
1.7251
0.1903
0.7913
-0.9850
-2.2671
-0.1501
-0.6011
-1.6646
-3.7993
0.8690
1.7897
273
0.6460
1.9104
-2.6329
-3.8386
1.4579
-2.9249
-4.2267
-4.2993
-2.5755
-5.0385
2.4305
2.9315
3.8105
1.3644
4.3031
2.5953
4.1849
1.5723
5.0540
-0.9447
2.5673
-0.7122
-1.9517
-1.5345
-0.6159
-0.1205
-2.0013
-4.7559
0.0869
0.5431
1.9934
4.7424
-0.0073
0.0941
0.0293
-0.0304
-2.2724
-1.3580
-2.1830
-0.6930
-2.6859
0.5480
-1.1772
0.4896
1.0423
0.9406
-1.2746
0.7341
-1.4804
-2.1866
0.5054
1.6178
-2.3533
-3.4272
1.2094
-2.5480
-3.8017
-3.7802
-2.2081
-4.4190
-2.4996
-1.0148
-0.0196
-0.1282
-1.7485
-4.2203
-0.1509
-0.5983
1.1264
2.9685
1.8080
4.4749
APPENDIX C (continued)
Fe(bpz)32+. BrNumber
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
Atom
Fe
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
N
N
N
N
N
N
N
N
N
N
N
N
Br
H
H
X
-0.4584
-0.1262
1.9681
0.5078
-1.5767
2.5828
-2.5470
-3.3016
-4.2464
1.5630
1.8296
2.6641
0.7704
2.9479
1.0332
-1.0716
-0.7922
-1.3051
0.0189
-1.4719
-1.8776
-0.1527
-2.6340
-2.1263
-2.8804
3.3580
1.1347
-0.2988
0.2609
-1.6259
-3.1350
-0.5614
-0.8998
-1.9690
-3.8718
0.6189
1.8634
3.2397
2.5688
-0.0521
274
Y
-0.3366
0.1087
-0.0810
0.2781
0.1144
0.1085
0.3438
-0.1160
0.1120
-1.9514
0.2834
-2.3046
-2.8839
-0.0988
-4.2655
-3.1292
-4.5008
1.9335
2.6321
3.2719
0.7753
3.9742
0.8339
-1.5525
-1.4665
-1.3808
-0.6399
-2.3179
-5.0718
-0.4387
-0.2740
1.6162
4.2965
-0.1202
0.3419
-0.0888
0.2747
2.3868
-0.2049
0.4183
Z
-0.0178
2.7910
1.7606
4.0311
2.5752
3.0234
3.5767
1.0100
2.0243
-1.2434
-1.8897
-2.0377
-0.4355
-2.6724
-0.2957
0.9878
1.1060
-1.5393
0.2619
-1.9259
-2.2338
-0.1603
-3.4260
-2.2355
-3.4176
-2.7575
-1.1836
0.2182
0.4656
-1.6382
-4.0160
-0.4199
-1.2362
1.2781
3.3095
1.6455
4.1524
0.1020
0.8752
4.9493
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
Fe(bpz)2(bpzN1)(Br)+
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
3.6632
-2.2646
-3.6124
-5.3098
1.5265
3.0117
3.5160
1.8743
-1.9117
-1.4093
0.6228
-2.0653
0.3366
-2.8394
-1.9273
-3.2817
0.1414
0.5374
-0.2973
0.1143
1.3157
-3.3289
0.6491
-4.7356
-2.6850
-5.1494
2.4045
3.5518
4.7809
1.7764
-2.5079
-2.3543
3.1048
4.6056
-0.0099
1.8115
-1.8414
-2.1166
-3.2135
-0.7932
1.5043
1.7180
1.1242
-2.7895
0.3731
-3.9212
-1.7694
-3.8940
X
-0.0720
-0.0106
1.9590
0.6402
-1.3876
2.5789
2.5230
0.1085
-2.3577
3.6126
-2.8760
-2.1630
-3.8491
-3.0818
-4.8356
2.2766
2.3733
3.4456
1.5639
3.5484
1.9576
3.8822
2.0058
4.0655
-0.2892
Y
0.1918
0.3539
-0.2030
0.0089
0.9034
-0.5156
-0.2927
0.1161
0.1918
-0.8427
2.6639
-0.8055
1.9389
3.6617
2.3476
-0.8581
1.4789
-0.8880
-2.0396
1.4204
2.4279
-1.8235
-3.3715
2.3256
-2.7987
Z
-0.1200
3.1231
2.0237
4.3410
3.2728
3.2389
1.1099
5.2804
4.0189
3.2718
3.0462
4.4013
3.7639
2.6715
3.9559
-1.3714
-1.3731
-2.1606
-0.8713
-2.1430
-1.0654
-2.4933
-1.0090
-2.4421
0.3415
(Low Spin)
Number
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
Atom
Fe
C
C
C
C
C
H
H
C
H
C
H
C
H
H
C
C
C
C
C
H
H
C
H
C
275
APPENDIX C (continued)
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
Fe(bpz)2(bpzN1)(Br)+
H
C
H
H
C
C
C
C
C
H
H
C
H
C
H
C
H
H
N
N
N
N
N
N
N
N
N
N
N
N
Br
2.9194
0.1798
-1.2138
-0.3671
-1.1123
-0.0633
-1.4724
-1.3905
-0.4166
0.4902
-2.0353
-2.1121
-0.1301
-1.1248
-2.5244
-1.8432
-0.7682
-2.0314
4.0831
1.7265
0.3974
1.3190
-0.8930
-2.3378
-0.4193
-1.1310
-1.6450
-3.5848
0.6563
1.9123
-2.4734
-3.6195
-4.1200
-2.5602
-4.9528
2.5308
3.0985
3.8802
1.4502
4.4457
2.7985
4.2105
1.5928
5.2128
-0.8218
2.5481
-0.6552
-1.7962
-1.4950
0.2404
0.3467
-1.7572
-4.4116
0.2254
0.5501
2.1390
4.8380
2.1537
0.7038
0.2117
-0.4318
-0.2996
-1.5384
0.1968
0.8527
0.6250
-1.3554
0.6543
-1.5353
-2.3062
0.4419
1.5283
-2.4010
-3.5093
1.1526
-2.7673
-3.8146
-3.9641
-2.4666
-4.6239
-2.5481
-0.9873
-0.1957
-0.4800
-1.9393
-4.3400
-0.2343
-0.6399
2.8108
4.2593
1.9239
4.4158
0.5361
X
-0.1823
0.0135
2.0319
0.7503
-1.4582
2.7397
2.5606
Y
-0.1084
-0.0166
0.0413
-0.2803
0.1458
-0.2016
0.1690
Z
0.1214
3.5235
2.3670
4.7092
3.6355
3.5534
1.4331
(High Spin)
Number
1
2
3
4
5
6
7
Atom
Fe
C
C
C
C
C
H
276
APPENDIX C (continued)
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
H
C
H
C
H
C
H
H
C
C
C
C
C
H
H
C
H
C
H
C
H
H
C
C
C
C
C
H
H
C
H
C
H
C
H
H
N
N
N
N
N
N
N
0.2378
-2.2350
3.8228
-3.3607
-1.7976
-4.1324
-3.8168
-5.2010
2.6050
2.1333
3.7240
2.2324
3.2642
1.4993
4.3646
3.0449
3.5396
0.6685
4.0022
1.4945
-0.2891
1.2041
-1.5766
-0.8539
-2.1933
-1.6146
-1.4705
-0.3570
-2.7381
-2.3097
-1.4302
-0.9826
-2.8577
-1.6782
-0.4776
-1.7133
4.0547
1.8015
1.0347
2.6817
-0.9467
-2.3381
-0.9057
277
-0.3888
-0.7789
-0.2599
1.4050
-1.6701
0.4767
2.2819
0.6080
-0.4369
1.8501
-0.1536
-1.7961
2.1126
2.6528
-0.9384
-2.9348
3.1245
-3.1473
-2.8741
-4.2673
-3.2221
-5.2527
2.2233
2.9071
3.4829
1.1478
4.1589
2.6617
3.7371
1.2449
4.9322
-1.0268
2.1362
-0.9117
-1.9441
-1.7295
1.1086
0.5841
-1.9143
-4.1643
-0.0012
0.2256
1.9490
5.6592
4.3719
3.5634
3.2351
4.8113
3.9658
2.7866
4.1001
-1.2704
-1.1929
-2.0903
-0.8306
-1.9882
-0.8392
-2.4767
-1.0344
-2.2649
0.2660
-1.5400
0.0488
0.7679
0.3959
-1.2711
0.8485
-1.4435
-2.2858
0.6503
1.7748
-2.3454
-3.5133
1.4094
-2.8527
-3.7971
-4.0714
-2.5760
-4.7829
-2.4452
-0.8361
-0.1727
-0.6005
-1.9722
-4.4031
-0.1082
APPENDIX C (continued)
51
52
53
54
55
56
N
N
N
N
N
Br
-2.1397 4.4458 -0.4925
-2.0271 1.2462 3.0748
-3.5680 -0.6153 4.5368
0.6699 0.1208 2.3254
2.0967 -0.3818 4.7340
-2.2692 -1.3756 0.6820
Fe(bpz)2(bpzN1)(Br)+ .Br- (High Spin)
Number
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
Atom
Fe
C
C
C
C
C
H
H
C
H
C
H
C
H
H
C
C
C
C
C
H
H
C
H
C
H
C
H
H
C
C
C
X
0.0637
0.0040
2.0947
0.6556
-1.4755
2.7206
2.6903
0.0798
-2.2931
3.8005
-3.3579
-1.8740
-4.1681
-3.7885
-5.2442
2.8979
2.4781
4.1194
2.4256
3.7232
1.8384
4.7884
3.1954
4.0638
0.7103
4.1939
1.4960
-0.2913
1.1303
-1.1962
-0.3597
-1.7355
278
Y
-0.0046
0.0249
0.1467
-0.1720
0.1656
-0.0254
0.2992
-0.2693
-0.7544
0.0038
1.4029
-1.6345
0.4817
2.2687
0.6076
-0.5105
1.7884
-0.2740
-1.8474
2.0039
2.6183
-1.0802
-3.0278
3.0106
-3.1205
-3.0102
-4.2772
-3.1435
-5.2448
2.4643
3.0037
3.7602
Z
-0.0218
3.326145
2.310951
4.564625
3.326018
3.560071
1.425878
5.478909
4.023223
3.645054
2.789402
4.500493
3.48401
2.29563
3.547149
-1.20949
-1.20736
-1.86431
-0.80515
-1.84857
-0.95797
-2.14304
-0.93571
-2.06009
0.149852
-1.35741
0.011156
0.563089
0.336896
-1.29816
0.822247
-1.40006
APPENDIX C (continued)
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
Fe(bpz)2Br2
C
C
H
H
C
H
C
H
C
H
H
N
N
N
N
N
N
N
N
N
N
N
N
Br
Br
-1.2942
-0.8878
0.1985
-2.2901
-1.9792
-0.7334
-0.7415
-2.4892
-1.4197
-0.2687
-1.4747
4.5326
2.0584
1.1703
2.7405
-0.6779
-2.0404
-0.5232
-1.5860
-2.0158
-3.6349
0.7405
2.0054
-2.1665
3.0709
1.4450
4.3087
2.7154
4.0865
1.6408
5.0503
-0.7134
2.5700
-0.4980
-1.6616
-1.2672
0.9814
0.5362
-1.9074
-4.2358
0.2527
0.6804
2.0920
4.6812
1.2548
-0.5987
0.1385
-0.2160
-1.2618
3.2961
-2.36689
0.684316
1.697756
-2.27258
-3.58947
1.459219
-3.06496
-3.81733
-4.27723
-2.83893
-5.03981
-2.19255
-0.90875
-0.25791
-0.53396
-2.12209
-4.54057
-0.16282
-0.41105
2.716387
4.106751
2.171097
4.690293
0.29756
1.500999
(High Spin)
Number
1
2
3
4
5
6
7
8
9
10
11
12
13
Atom
Fe
C
C
C
C
C
H
H
C
H
C
H
C
X
-0.0369
-0.1068
2.1140
0.3463
-1.5318
2.5474
2.8154
-0.3416
-2.5980
3.6020
-3.0711
-2.4340
-4.1196
279
Y
Z
0.2088 -0.1467
-0.0054 2.9639
-0.0278 2.2481
-0.0169 4.3034
0.0568 2.5697
-0.0291 3.5867
-0.0176 1.4221
-0.0130 5.1416
0.1878 3.4858
-0.0283 3.8404
0.1314 0.8085
0.2269 4.5569
0.2628 1.7421
APPENDIX C (continued)
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
Fe(NCCH3)4Br2
H
H
C
C
C
C
C
H
H
C
H
C
H
C
H
H
N
N
N
N
N
N
N
N
Br
Br
-3.2292
-5.1504
2.1499
2.4343
3.2260
1.3572
3.4980
2.0989
3.5511
1.5967
4.0307
-0.4738
2.4158
-0.2222
-1.3126
-0.8522
1.6632
0.7976
-1.7885
-3.8868
0.3135
0.8199
1.7662
3.9039
-1.4960
0.1385
0.1173
0.3524
-1.2470
1.0692
-1.4276
-2.3511
0.8614
2.0587
-2.4152
-3.7218
1.6986
-2.9627
-4.0471
-4.3165
-2.6549
-5.1021
-0.0311
-0.0203
0.0207
0.2854
-1.9868
-4.7001
0.0180
-0.3858
-0.1156
2.7174
-0.2656
1.4174
-1.6679
-1.8461
-2.5654
-1.0992
-2.7406
-1.5567
-2.8738
-1.3595
-3.1778
0.2158
-1.9910
-0.0589
0.8280
0.3438
4.6166
1.9426
1.2271
3.0781
-0.2955
-0.8438
-1.3020
-3.0993
-2.2879
0.2457
X
-0.2431
-0.6305
2.2992
-0.4858
-0.3932
-2.4693
-3.6247
-0.1720
0.1090
-0.1788
0.0961
0.5321
Y
0.0057
0.0247
-0.0020
-0.0096
-0.0165
0.0073
0.0074
2.1594
3.2631
-2.1472
-3.2484
4.6059
Z
-0.2687
2.3057
-0.8267
-2.4794
-3.6444
-0.3624
-0.1861
-0.2150
0.0431
-0.1839
0.0905
0.4361
(High Spin)
Number
1
2
3
4
5
6
7
8
9
10
11
12
Atom
Fe
Br
Br
N
C
N
C
N
C
N
C
C
280
APPENDIX C (continued)
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
H
H
H
C
H
H
H
C
H
H
H
C
H
H
H
1.5967
-0.0410
0.3862
-0.1770
-0.6393
-0.6057
0.8994
0.5126
-0.0419
1.5837
0.3364
-5.0516
-5.5312
-5.5497
-5.1786
4.7370
5.3736
4.7362
-0.0251
-0.9082
0.8723
-0.0458
-4.5873
-5.3603
-4.7153
-4.7122
0.0072
0.9198
-0.8592
-0.0385
0.2107
-0.0954
1.5146
-5.0910
-5.5459
-5.5510
-5.2980
0.5035
-0.0399
0.3094
1.5781
0.1355
-0.2357
-0.3136
1.2235
Energy for molecules used mechanism
Molecule
Fe(bpz)32+
Fe(bpz)32+. BrFe(bpz)2(bpzN1)(Br)+
Fe(bpz)2(bpzN1)(Br)+
Fe(bpz)2(bpzN1)(Br)+ .BrFe(bpz)2(bpzN1)(Br)+ .BrFe(NCCH3)4Br2
(Low Spin)
(High Spin)
(High Spin)
(High Spin)
(High Spin)
Acetonitrile
Bromide
Bpz
Energy
-1705.58985957
-1719.28849766
-1719.26521385
-1719.28373808
-1732.88694750
-1205.56523800
-681.81869539
-132.72854294
-13.47199470
-527.32176150
281
APPENDIX D
CHAPTER 5 SUPPLEMENTARY INFORMATION
Optimized Geometries for all four complexes.
Complex 1: E(RB+HF-LYP) = -1609.55604228 au
Atom
Fe
C
C
C
C
C
H
H
C
H
C
H
C
H
H
C
C
C
C
C
H
H
C
H
C
H
C
H
H
C
C
C
Coordinates (Angstroms)
X
Y
Z
0.000022 -0.000149 0.000428
0.002399 -0.000181 2.870353
2.211818 -0.002744 2.062849
0.463498 -0.036789 4.198996
-1.425155 0.023621 2.491734
2.734930 -0.036260 3.363656
2.869609 0.015208 1.204058
-0.235925 -0.055166 5.026531
-2.483934 0.070027 3.417067
3.809187 -0.048747 3.512505
-2.944400 0.013815 0.695449
-2.286435 0.096800 4.482205
-4.043047 0.056655 1.565975
-3.090691 -0.013173 -0.376228
-5.050008 0.067605 1.163166
2.165135 -1.400673 -1.260062
2.440753 0.920058 -1.530315
3.332049 -1.649370 -2.005698
1.320616 -2.459076 -0.669521
3.612772 0.738882 -2.278722
2.067529 1.914176 -1.322745
3.666232 -2.664071 -2.187415
1.618171 -3.832524 -0.736359
4.148919 1.601988 -2.658128
-0.645507 -2.904959 0.543300
2.513590 -4.180433 -1.237780
-0.406345 -4.286372 0.509656
-1.525698 -2.510033 1.033308
-1.106477 -4.966359 0.982725
-0.811052 2.449730 -1.256948
0.297108 2.910958 0.766475
-1.033454 3.821778 -1.474599
282
APPENDIX D (continued)
C
C
H
H
C
H
C
H
C
H
H
N
N
N
N
N
N
C
C
C
C
C
C
H
H
H
H
H
H
-1.253393
0.109637
0.817990
-1.562127
-1.897309
0.485437
-1.360095
-2.096107
-2.007291
-1.139432
-2.285296
1.723779
0.192044
-0.987434
-0.147690
-1.658081
0.875874
-2.280063
-0.569648
-3.809162
1.844419
4.066787
0.747816
4.968221
0.965256
2.214678
-4.636170
-2.776582
-0.734712
1.384519
4.291548
2.522164
4.162807
1.624259
4.977404
-0.938712
2.636584
-0.766717
-1.929992
-1.634300
-0.119692
-2.000552
0.106726
1.999600
-0.004549
0.016804
0.539414
4.756516
0.086796
-0.055201
-0.570408
-4.759880
-0.746877
-5.822442
-0.084349
0.123342
0.709107
5.818168
-2.179750
0.606327
1.631508
-2.356914
-3.407489
1.357816
-2.533583
-3.739105
-3.765743
-2.160497
-4.354280
-1.025429
-0.031828
-1.747459
-0.139951
1.136993
1.808726
-4.212734
-0.534988
2.953287
4.453085
-2.523008
-0.141228
-3.101269
-0.183585
5.472967
3.655315
-5.162884
-0.689168
Complex 2: E(RB+HF-LYP) = -1705.5898596 au
Atom
Fe
C
C
C
C
Coordinates (Angstroms)
X
Y
Z
-0.002332 -0.003152 0.000213
-0.013292 0.013858 2.864027
2.196898 0.014802 2.095943
0.466860 -0.017292 4.191518
-1.431567 0.030592 2.482038
283
APPENDIX D (continued)
C
H
H
C
H
C
H
C
H
H
C
C
C
C
C
H
H
C
H
C
H
C
H
H
C
C
C
C
C
H
H
C
H
C
H
C
H
H
N
N
2.651945
2.896389
-0.204184
-2.513238
3.711729
-2.957260
-2.360960
-4.019893
-3.147728
-5.052723
2.166392
2.459791
3.343106
1.326065
3.632311
2.121608
3.712260
1.609829
4.221219
-0.629111
2.499520
-0.325769
-1.525391
-0.979291
-0.813341
0.277986
-1.030088
-1.248817
0.052280
0.803327
-1.554167
-1.890385
0.394948
-1.363208
-2.106032
-2.005018
-1.162960
-2.309639
4.072826
1.725107
-0.012822
0.030823
-0.036434
0.082239
-0.022265
0.006325
0.118821
0.054805
-0.027413
0.063425
-1.404694
0.898174
-1.632264
-2.456050
0.646034
1.910368
-2.632889
-3.838597
1.457900
-2.924915
-4.226690
-4.299295
-2.575496
-5.038517
2.430509
2.931491
3.810541
1.364427
4.303089
2.595341
4.184850
1.572332
5.053973
-0.944706
2.567279
-0.712194
-1.951683
-1.534471
-0.615851
-0.120485
284
3.428825
1.271340
5.043631
3.388185
3.660522
0.707822
4.461557
1.631363
-0.356269
1.299518
-1.238527
-1.533471
-1.985079
-0.649765
-2.272408
-1.357990
-2.182990
-0.692953
-2.685913
0.547964
-1.177203
0.489581
1.042322
0.940570
-1.274623
0.734088
-1.480376
-2.186601
0.505372
1.617762
-2.353264
-3.427177
1.209408
-2.547997
-3.801700
-3.780230
-2.208147
-4.418965
-2.499589
-1.014794
APPEDIX D (continued)
N
N
N
N
N
N
N
N
N
N
0.190265
0.791258
-0.985021
-2.267112
-0.150147
-0.601138
-1.664627
-3.799306
0.869007
1.789698
-2.001310
-4.755887
0.086855
0.543078
1.993413
4.742389
-0.007345
0.094078
0.029305
-0.030434
-0.019627
-0.128229
-1.748505
-4.220321
-0.150865
-0.598343
1.126360
2.968514
1.808048
4.474910
Complex 3: E(RB+HF-LYP) = -1838.2204786 au
Atom
Fe
C
C
C
C
H
H
C
C
H
H
C
C
C
C
H
H
C
C
H
H
C
C
C
Coordinates (Angstroms)
X
Y
Z
0.000730 -0.006953 -0.003886
-0.052379 0.013124 2.839710
2.177598 0.107158 2.145960
-1.431162 -0.048826 2.453546
2.623490 0.120541 3.491018
2.890530 0.143180 1.331650
3.688196 0.160508 3.693493
-2.976696 -0.136988 0.702324
-4.056069 -0.158391 1.620396
-3.163079 -0.167461 -0.364083
-5.071132 -0.198746 1.240633
2.221237 -1.323538 -1.196097
2.489187 0.979961 -1.488067
1.414707 -2.383608 -0.667202
3.704244 0.776708 -2.188474
2.113110 1.981909 -1.322148
4.248475 1.637454 -2.561476
-0.531018 -2.983498 0.480953
-0.193062 -4.356797 0.390295
-1.444584 -2.675080 0.974028
-0.858695 -5.093906 0.825970
-0.870173 2.380088 -1.282088
0.192229 2.962936 0.716796
-1.279465 1.327756 -2.164732
285
APPENDIX D (continued)
C
H
H
C
C
H
H
N
N
N
N
N
N
C
C
C
C
C
C
H
H
H
H
H
H
C
C
C
C
H
H
C
C
C
C
H
H
C
C
C
-0.054086
0.718376
0.285719
-1.346185
-2.020379
-1.106763
-2.287264
1.757202
0.246566
-0.982338
-0.199777
-1.688660
0.870771
-2.331037
-0.724890
-3.799809
1.692740
4.181459
0.983287
5.112289
1.257185
2.016145
-4.614417
-2.850427
-0.920062
-1.958524
-1.153786
-2.234283
-1.850212
-2.065269
-2.754513
-2.451151
0.305517
-2.069548
-0.744324
-2.850853
-0.468392
1.827228
3.431640
3.063432
4.337973
2.646746
5.068898
-0.971681
-0.758327
-1.975911
-1.613779
-0.040258
-2.010195
0.041418
1.997212
-0.086409
0.057715
0.540764
4.730315
-0.129169
0.083893
-0.519254
-4.739496
-0.693751
-5.787636
0.096376
-0.148094
0.723163
5.779934
1.632598
3.735196
3.016248
4.026684
5.063186
3.246762
-0.074454
0.030159
-0.049196
-0.002946
-0.069899
0.011787
-3.736377
-1.618380
-4.017629
286
0.477720
1.609139
1.203308
-2.578469
-3.806556
-2.251498
-4.417441
-0.995550
-0.035856
-1.765883
-0.139197
1.099078
1.815934
-4.209578
-0.681090
2.991544
4.529663
-2.386464
-0.254915
-2.918788
-0.336317
5.566746
3.710082
-5.146187
-0.882251
-3.375688
-1.604068
-3.689632
-2.836614
-3.081100
-4.615131
3.443289
4.215286
4.837126
5.208135
5.591757
6.258850
-0.809523
-1.880699
-1.503678
APPENDIX D (continued)
C
H
H
3.832912
3.376296
4.758782
-2.999799
-5.052366
-3.222701
-2.021305
-1.612202
-2.544192
Complex 4: E(RB+HF-LYP) = -1608.362025 au
Atom
Fe
C
C
C
C
H
C
C
H
H
C
C
C
C
H
H
C
C
H
H
C
C
C
C
H
H
C
C
H
N
N
Coordinates (Angstroms)
X
Y
Z
0.018201 -0.014333 -0.009026
-0.050184 0.026153 2.825723
2.119257 0.290913 1.871434
-1.464541 -0.163191 2.441133
2.701402 0.387719 3.148013
3.769611 0.527467 3.268745
-2.936277 -0.384972 0.617089
-4.041479 -0.511214 1.473478
-3.062616 -0.420178 -0.458288
-5.033792 -0.645716 1.056896
2.803870 0.357877 0.563470
2.484951 0.276759 -1.767547
-0.332710 -2.453054 -1.478114
3.858312 0.450507 -2.001163
1.792157 0.173107 -2.593846
4.232428 0.481083 -3.018712
0.640560 -2.928439 0.612094
0.677127 -4.302438 0.326599
1.010017 -2.549610 1.557411
1.079262 -4.994639 1.058361
-0.934902 2.199648 -1.564080
-0.126412 2.981779 0.504066
-1.149443 0.992996 -2.389885
-0.435185 4.309237 0.167420
0.319998 2.743529 1.461960
-0.224904 5.106928 0.871527
-0.843388 -1.371410 -2.346126
-1.392446 -1.496337 -3.635007
-1.484258 -2.464243 -4.114441
1.956896 0.229597 -0.519203
0.149508 -2.014308 -0.261317
287
APPENDIX D (continued)
N
N
N
N
C
C
C
C
C
C
H
H
H
H
H
H
C
C
C
C
C
C
H
H
H
H
H
H
-0.736460
-0.365224
-1.671914
0.773729
-1.825312
-1.014974
-3.834410
1.866558
4.724446
0.187163
5.791184
0.201458
2.295276
-4.668227
-2.251909
-1.265021
-1.706589
-1.267394
-2.527364
0.477929
-0.323680
4.186558
4.836701
-0.707121
-2.040558
-1.714513
-0.162658
-2.345412
-0.144406
1.941901
-0.214437
0.114132
-0.332249
4.576150
-0.459565
0.299283
0.581915
-4.753460
0.717469
-5.809476
0.371735
-0.553933
-0.405799
5.591741
0.927014
3.504710
-0.283141
0.117339
-3.813516
0.534659
0.634049
-4.139707
1.821395
3.688270
0.049642
-0.240600
-1.762328
-0.333308
1.077332
1.743256
-4.300250
-1.085927
2.863707
4.279465
-0.900815
-0.912313
-1.048250
-1.162668
5.273952
3.552105
-5.295558
-1.375941
-3.679537
-1.960372
3.350387
4.126111
-1.824329
0.397202
1.259456
-2.784830
-4.193061
-2.931134
4.998062
4.418595
Molecular Orbital Energies and Percent Contributions for Complexes 1 – 4.
Complex 1
MO
151
150
149
148
147
L+20
L+19
L+18
L+17
L+16
Energy
(eV)
-2.82
-2.86
-2.97
-3.96
-3.97
%Fe
0.728
0.518
91.96
80.57
80.52
%Bpy
56.00
32.44
2.575
6.790
6.100
288
%Bpy
1.485
33.68
2.699
6.360
6.660
%Bpy
41.78
33.36
2.758
6.280
6.720
%Total
100
100
100
100
100
Type
L
L
Fe
Fe
Fe
APPENDIX D (continued)
146
145
144
143
142
141
140
139
138
137
136
135
134
133
132
131
130
129
128
127
126
125
124
123
122
121
120
L+15
L+14
L+13
L+12
L+11
L+10
L+9
L+8
L+7
L+6
L+5
L+4
L+3
L+2
L+1
LUMO
HOMO
H-1
H-2
H-3
H-4
H-5
H-6
H-7
H-8
H-9
H-10
-4.08
-4.90
-5.05
-5.05
-5.22
-5.22
-5.43
-6.52
-6.53
-6.69
-6.69
-6.69
-6.98
-7.66
-7.67
-7.67
-11.38
-11.44
-11.44
-12.48
-12.48
-12.56
-13.64
-13.64
-13.67
-13.92
-13.92
77.15
97.80
76.58
76.54
1.720
1.752
2.859
0.466
0.469
2.755
2.741
1.948
0.812
0.067
3.800
3.800
87.16
84.61
84.62
0.420
0.420
1.876
0.223
0.222
0.102
1.369
1.373
7.690
0.720
8.842
6.786
30.62
35.06
32.20
47.42
19.15
6.806
59.18
31.43
32.94
34.97
61.42
1.063
4.248
7.226
3.047
60.58
6.085
32.43
32.46
34.38
33.10
26.44
39.53
7.580
0.750
4.283
11.33
61.85
3.604
32.44
50.92
15.54
60.64
3.502
33.25
33.09
33.66
23.10
40.67
4.303
3.208
7.027
35.53
30.99
32.57
52.90
13.69
33.14
12.02
53.59
7.580
0.730
10.29
5.348
5.804
59.58
32.50
1.193
64.84
29.80
34.57
33.37
33.16
31.30
11.68
54.47
4.286
4.957
5.301
3.468
62.51
33.12
14.41
51.71
33.66
60.17
5.510
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
Fe
Fe
Fe
Fe
L
L
L
L
L
L
L
L
L
L
L
L
Fe
Fe
Fe
L
L
L
L
L
L
L
L
L+20
L+19
L+18
L+17
L+16
L+15
L+14
L+13
L+12
L+11
Energy
(eV)
-4.25
-4.25
-4.31
-5.02
-5.03
-5.09
-5.72
-6.62
-6.62
-6.69
%Fe
1.320
1.317
0.381
85.41
85.34
79.87
93.99
3.237
3.267
75.23
%Bpz
47.77
18.40
32.82
6.130
3.600
6.770
1.960
52.88
11.69
7.745
%Bpz
50.64
14.92
33.45
4.520
5.250
6.700
2.030
42.82
21.75
6.053
%Bpz
0.273
65.37
33.34
3.940
5.810
6.660
2.020
1.062
63.29
10.97
%Total
100
100
100
100
100
100
100
100
100
100
Type
L
L
L
Fe
Fe
Fe
Fe
L
L
Fe
Complex 2
MO
151
150
149
148
147
146
145
144
143
142
289
APPENDIX D (continued)
141
140
139
138
137
136
135
134
133
132
131
130
129
128
127
126
125
124
123
122
121
120
L+10
L+9
L+8
L+7
L+6
L+5
L+4
L+3
L+2
L+1
LUMO
HOMO
H-1
H-2
H-3
H-4
H-5
H-6
H-7
H-8
H-9
H-10
-6.69
-6.85
-8.11
-8.11
-8.19
-8.19
-8.32
-8.41
-9.20
-9.25
-9.25
-13.05
-13.11
-13.11
-13.40
-13.43
-13.43
-13.46
-13.46
-13.48
-13.84
-13.84
L+20
L+19
L+18
L+17
L+16
L+15
L+14
L+13
L+12
L+11
L+10
L+9
L+8
L+7
L+6
Energy
(eV)
-3.86
-3.86
-4.01
-4.06
-4.06
-4.22
-4.78
-4.93
-4.93
-5.32
-5.32
-5.42
-5.98
-5.98
-6.24
75.16
3.492
2.737
2.745
0.388
0.393
2.248
0.582
0.175
4.604
4.601
86.51
83.18
83.18
0.000
2.499
2.488
1.902
1.907
0.776
0.826
0.827
8.833
32.05
62.72
2.147
56.72
10.00
32.32
33.06
33.71
61.38
1.790
4.485
4.974
6.239
33.89
31.76
34.33
32.65
31.70
32.54
59.19
7.159
10.41
32.17
16.72
48.23
38.26
28.09
32.53
33.14
33.32
9.649
53.90
4.506
4.902
6.291
33.08
24.12
40.80
22.52
42.55
33.83
37.15
29.16
5.601
32.29
17.83
46.88
4.628
61.52
32.89
33.22
32.79
24.37
39.71
4.497
6.944
4.285
33.23
41.63
22.38
42.93
23.85
32.86
2.834
62.85
%Phen
6.460
6.470
8.970
56.77
7.494
32.76
1.550
3.504
10.96
43.87
22.63
32.07
0.309
64.74
32.89
%Phen
6.330
6.640
8.900
2.086
61.53
33.39
1.480
9.593
4.893
0.895
64.70
32.99
52.02
12.57
33.34
%Phen
6.590
6.290
8.940
37.06
26.80
33.09
1.460
8.628
5.844
54.44
11.89
32.26
44.91
19.93
33.08
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
Fe
L
L
L
L
L
L
L
L
L
L
Fe
Fe
Fe
L
L
L
L
L
L
L
L
Complex 3
MO
169
168
167
166
165
164
163
162
161
160
159
158
157
156
155
%Fe
80.62
80.60
73.19
4.081
4.177
0.755
95.51
78.27
78.30
0.799
0.772
2.684
2.766
2.756
0.691
290
%Total
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
Type
Fe
Fe
Fe
L
L
L
Fe
Fe
Fe
L
L
L
L
L
L
APPENDIX D (continued)
154
153
152
151
150
149
148
147
146
145
144
143
142
141
140
139
138
L+5
L+4
L+3
L+2
L+1
LUMO
HOMO
H-1
H-2
H-3
H-4
H-5
H-6
H-7
H-8
H-9
H-10
-7.22
-7.22
-7.36
-7.42
-7.46
-7.46
-11.25
-11.25
-11.25
-12.07
-12.07
-12.07
-12.46
-12.46
-12.55
-13.78
-13.78
0.124
0.124
1.415
0.039
3.722
3.719
86.46
78.29
78.38
0.166
8.479
8.407
1.848
1.845
3.421
0.278
0.280
45.60
21.45
32.24
34.03
23.76
39.87
3.670
11.94
3.346
40.11
45.33
8.896
53.58
12.24
31.78
45.64
20.95
3.264
62.84
33.46
32.33
12.44
52.61
5.126
3.443
10.40
24.65
3.928
65.71
2.452
62.61
32.59
22.73
43.57
51.01
15.59
32.88
33.60
60.07
3.804
4.740
6.337
7.875
35.07
42.26
16.98
42.12
23.31
32.21
31.35
35.19
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
L
L
L
L
L
L
Fe
Fe
Fe
L
L
L
L
L
L
L
L
Complex 4
MO
150
149
148
147
146
145
144
143
142
141
140
139
138
137
136
135
134
133
132
131
L+20
L+19
L+18
L+17
L+16
L+15
L+14
L+13
L+12
L+11
L+10
L+9
L+8
L+7
L+6
L+5
L+4
L+3
L+2
L+1
Energy
(eV)
-3.08
-3.08
-3.15
-3.85
-3.85
-4.35
-4.87
-4.97
-5.05
-5.06
-5.40
-5.93
-5.93
-6.63
-6.63
-6.63
-6.68
-7.64
-7.67
-7.83
%Fe
2.130
2.134
89.30
77.27
77.21
78.93
90.96
0.000
1.207
89.26
78.97
2.474
2.473
1.292
1.213
3.259
0.001
2.791
0.000
4.389
%Tpy
49.45
48.43
5.357
15.75
7.010
10.53
4.508
49.78
49.61
5.322
10.57
12.39
85.14
38.02
66.16
42.77
50.17
48.03
50.58
14.76
291
%Tpy
48.42
49.44
5.342
6.980
15.78
10.54
4.527
50.22
49.18
5.422
10.46
85.14
12.39
60.69
32.63
53.97
49.83
49.18
49.42
80.85
%Total
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
Type
L
L
Fe
Fe
Fe
Fe
Fe
L
L
Fe
Fe
L
L
L
L
L
L
L
L
L
APPENDIX D (continued)
130
129
128
127
126
125
124
123
122
121
120
119
LUMO
HOMO
H-1
H-2
H-3
H-4
H-5
H-6
H-7
H-8
H-9
H-10
-7.83
-11.43
-11.55
-11.55
-12.38
-12.44
-13.19
-13.19
-13.60
-13.69
-13.69
-14.24
4.387
77.74
81.68
81.71
0.000
3.195
2.121
2.116
0.000
0.730
0.727
6.458
80.86
11.11
7.747
10.54
49.84
48.57
20.84
77.04
50.03
13.17
86.12
63.74
14.76
11.15
10.57
7.753
50.16
48.23
77.04
20.84
49.97
86.10
13.15
29.81
100
100
100
100
100
100
100
100
100
100
100
100
L
Fe
Fe
Fe
L
L
L
L
L
L
L
L
Calculated singlet excited-states in the gas phase. The excited state number is followed by
the spin multiplicity, symmetry, excitation energy and oscillator strength f. The excitations
from occupied to virtual orbitals follow on the next line, followed by the wavefunction
coefficients.
Complex 1:
Excited State 1: Singlet-?Sym 2.3667 eV 523.87 nm f=0.0006
128 ->143
-0.29520
129 ->144
-0.29428
130 ->131
-0.14838
130 ->132
-0.11737
130 ->144
0.52383
This state for optimization and/or second-order correction.
Total Energy, E(RPA) = -1609.46906748
Copying the excited state density for this state as the 1-particle RhoCI density.
Excited state symmetry could not be determined.
Excited State 2: Singlet-?Sym 2.3678 eV 523.62 nm f=0.0006
128 ->144
-0.29769
129 ->143
0.29550
130 ->131
-0.11777
130 ->132
0.14707
130 ->143
0.52110
Excited state symmetry could not be determined.
Excited State 7: Singlet-?Sym 2.7972 eV 443.24 nm f=0.0230
128 ->131
0.44470
128 ->132
0.11638
292
APPENDIX D (continued)
129 ->131
129 ->132
129 ->133
130 ->131
-0.11788
0.44907
0.15317
0.15618
Excited state symmetry could not be determined.
Excited State 8: Singlet-?Sym 2.7978 eV 443.15 nm f=0.0232
128 ->131
-0.12028
128 ->132
0.44677
128 ->133
-0.16246
129 ->131
-0.44360
129 ->132
-0.11981
130 ->132
-0.15110
Excited state symmetry could not be determined.
Excited State 9: Singlet-?Sym 2.8561 eV 434.10 nm f=0.0001
130 ->133
0.69959
Excited state symmetry could not be determined.
Excited State 10: Singlet-?Sym 2.9623 eV 418.55 nm f=0.0485
128 ->132
0.10422
128 ->133
0.53648
129 ->131
-0.10435
129 ->133
-0.41296
Excited state symmetry could not be determined.
Excited State 11: Singlet-?Sym 2.9623 eV 418.54 nm f=0.0487
128 ->133
0.41520
129 ->133
0.54035
Excited state symmetry could not be determined.
Excited State 13: Singlet-?Sym 3.4892 eV 355.34 nm f=0.0031
128 ->135
-0.11145
128 ->144
0.29323
129 ->143
-0.29208
130 ->143
0.38460
Excited state symmetry could not be determined.
Excited State 14: Singlet-?Sym 3.4901 eV 355.25 nm f=0.0032
128 ->143
0.29439
129 ->135
0.10330
129 ->144
0.29386
130 ->144
0.38195
293
APPENDIX D (continued)
Excited state symmetry could not be determined.
Excited State 16: Singlet-?Sym 3.6069 eV 343.74 nm f=0.0040
130 ->134
0.69533
Excited state symmetry could not be determined.
Excited State 17: Singlet-?Sym 3.6832 eV 336.62 nm f=0.0055
129 ->134
0.69562
Excited state symmetry could not be determined.
Excited State 18: Singlet-?Sym 3.6835 eV 336.59 nm f=0.0055
128 ->134
0.69562
Excited state symmetry could not be determined.
Excited State 19: Singlet-?Sym 3.8698 eV 320.39 nm f=0.0066
128 ->135
0.54466
129 ->135
-0.25016
130 ->136
0.15877
130 ->137
0.28944
Excited state symmetry could not be determined.
Excited State 20: Singlet-?Sym 3.8698 eV 320.39 nm f=0.0066
128 ->135
0.24871
129 ->135
0.54663
130 ->136
-0.29345
130 ->137
0.16071
Excited state symmetry could not be determined.
Excited State 21: Singlet-?Sym 3.9018 eV 317.76 nm f=0.0033
128 ->135
-0.28507
130 ->136
0.11570
130 ->137
0.57492
Excited state symmetry could not be determined.
Excited State 22: Singlet-?Sym 3.9019 eV 317.75 nm f=0.0032
129 ->135
0.30263
130 ->136
0.57390
130 ->137
-0.11721
Excited state symmetry could not be determined.
Excited state symmetry could not be determined.
Excited State 25: Singlet-?Sym 3.9873 eV 310.95 nm f=0.0025
128 ->136
-0.47132
129 ->137
0.47929
294
APPENDIX D (continued)
130 ->138
0.10724
Excited state symmetry could not be determined.
Excited State 26: Singlet-?Sym 3.9874 eV 310.94 nm f=0.0026
128 ->137
0.46960
129 ->136
0.47938
130 ->139
-0.10579
Excited state symmetry could not be determined.
Excited State 27: Singlet-?Sym 4.0319 eV 307.51 nm f=0.0291
130 ->138
0.67428
Excited state symmetry could not be determined.
Excited State 28: Singlet-?Sym 4.0324 eV 307.47 nm f=0.0290
130 ->139
0.67441
Excited state symmetry could not be determined.
Excited State 30: Singlet-?Sym 4.0754 eV 304.22 nm f=0.0005
126 ->131
0.15355
127 ->132
-0.15284
128 ->138
0.33480
128 ->139
-0.32424
129 ->138
-0.32535
129 ->139
-0.33156
Excited state symmetry could not be determined.
Excited State 31: Singlet-?Sym 4.1052 eV 302.02 nm f=0.0142
128 ->138
0.37243
128 ->139
-0.27870
129 ->138
0.27898
129 ->139
0.37490
130 ->138
0.11716
Excited state symmetry could not be determined.
Excited State 32: Singlet-?Sym 4.1054 eV 302.00 nm f=0.0144
128 ->138
0.27912
128 ->139
0.37705
129 ->138
-0.37130
129 ->139
0.27803
130 ->139
-0.11735
Excited state symmetry could not be determined.
Excited State 34: Singlet-?Sym 4.2707 eV 290.31 nm f=0.0172
295
APPENDIX D (continued)
126 ->131
126 ->132
127 ->131
127 ->132
127 ->133
0.30536
-0.28897
0.28142
0.30838
0.36889
Excited state symmetry could not be determined.
Excited State 35: Singlet-?Sym 4.2713 eV 290.27 nm f=0.0173
126 ->131
-0.27611
126 ->132
-0.30463
126 ->133
0.38290
127 ->131
0.29910
127 ->132
-0.28521
Excited state symmetry could not be determined.
Excited State 36: Singlet-?Sym 4.3160 eV 287.27 nm f=0.0001
111 ->143
-0.10528
112 ->144
0.10551
126 ->132
-0.17738
127 ->131
-0.19506
128 ->137
-0.24805
128 ->138
-0.18166
128 ->139
-0.18265
129 ->136
0.24820
129 ->138
-0.18161
129 ->139
0.18154
130 ->135
0.27066
Excited state symmetry could not be determined.
Excited State 37: Singlet-?Sym 4.3169 eV 287.20 nm f=0.0028
125 ->131
0.51429
125 ->132
0.14700
126 ->131
-0.16103
126 ->132
-0.13138
126 ->133
-0.38606
Excited state symmetry could not be determined.
Excited State 38: Singlet-?Sym 4.3178 eV 287.15 nm f=0.0023
125 ->131
-0.16266
125 ->132
0.52143
126 ->131
-0.13597
127 ->133
0.39488
296
APPENDIX D (continued)
Excited state symmetry could not be determined.
Excited State 39: Singlet-?Sym 4.3199 eV 287.01 nm f=0.0296
125 ->133
0.47317
126 ->131
-0.29983
127 ->132
0.36232
Excited state symmetry could not be determined.
Excited State 40: Singlet-?Sym 4.4683 eV 277.48 nm f=0.1977
125 ->131
0.37058
126 ->131
0.10283
126 ->132
0.15263
126 ->133
0.36726
126 ->134
0.14407
127 ->131
-0.14516
Excited state symmetry could not be determined.
Excited State 41: Singlet-?Sym 4.4686 eV 277.46 nm f=0.1977
125 ->132
-0.36975
126 ->131
-0.14719
127 ->132
-0.14086
127 ->133
0.37509
127 ->134
0.14389
Excited state symmetry could not be determined.
Excited State 42: Singlet-?Sym 4.5780 eV 270.83 nm f=0.6547
125 ->133
0.45687
126 ->131
0.23965
127 ->132
-0.23998
128 ->138
-0.10088
129 ->139
0.10108
Excited state symmetry could not be determined.
Excited State 43: Singlet-?Sym 4.9549 eV 250.23 nm f=0.0277
124 ->133
0.11177
127 ->133
-0.10187
127 ->134
0.63674
Excited state symmetry could not be determined.
Excited State 44: Singlet-?Sym 4.9552 eV 250.21 nm f=0.0277
123 ->133
-0.10841
126 ->134
0.63650
Excited state symmetry could not be determined.
297
APPENDIX D (continued)
Excited State 45: Singlet-?Sym
123 ->131
-0.12296
123 ->132
-0.10436
124 ->131
0.10472
124 ->132
-0.12205
125 ->134
0.63081
5.0196 eV 247.00 nm f=0.0303
Excited state symmetry could not be determined.
Excited State 46: Singlet-?Sym 5.1114 eV 242.56 nm f=0.0017
122 ->131
0.31291
123 ->132
0.10416
124 ->131
0.10355
124 ->133
0.10073
125 ->138
-0.15324
126 ->135
0.46373
126 ->138
-0.13537
127 ->139
-0.13262
130 ->141
0.10496
Excited state symmetry could not be determined.
Excited State 47: Singlet-?Sym 5.1116 eV 242.55 nm f=0.0017
122 ->132
-0.31028
123 ->131
-0.10287
123 ->133
0.10533
124 ->132
0.10646
125 ->139
0.15194
126 ->139
-0.13569
127 ->135
0.46592
127 ->138
0.13573
130 ->142
0.10476
Excited state symmetry could not be determined.
Excited State 49: Singlet-?Sym 5.2032 eV 238.28 nm f=0.0056
123 ->132
0.10026
124 ->133
-0.12873
125 ->136
-0.15264
126 ->137
-0.31577
127 ->134
0.14799
127 ->136
-0.32409
128 ->140
0.16928
129 ->140
0.36561
Excited state symmetry could not be determined.
298
APPENDIX D (continued)
Excited State 50: Singlet-?Sym
123 ->133
0.12332
124 ->132
-0.10156
125 ->137
0.15315
126 ->134
0.14817
126 ->136
0.31141
127 ->137
-0.31950
128 ->140
0.36587
129 ->140
-0.17041
No.
1
2
7
8
9
10
11
13
14
16
17
18
19
20
21
22
25
26
27
28
30
31
32
34
35
36
37
38
39
40
41
Energy
(eV)
2.3667
2.3678
2.7972
2.7978
2.8561
2.9623
2.9623
3.4892
3.4901
3.6069
3.6832
3.6835
3.8698
3.8698
3.9018
3.9019
3.9873
3.9874
4.0319
4.0324
4.0754
4.1052
4.1054
4.2707
4.2713
4.3160
4.3169
4.3178
4.3199
4.4683
4.4686
5.2035 eV 238.27 nm f=0.0056
Wavelength(nm)
523.87
523.62
443.24
443.15
434.10
418.55
418.54
355.34
355.25
343.74
336.62
336.59
320.39
320.39
317.76
317.75
310.95
310.94
307.51
307.47
304.22
302.02
302.00
290.31
290.27
287.27
287.20
287.15
287.01
277.48
277.46
f
0.0006
0.0006
0.0230
0.0232
0.0001
0.0485
0.0487
0.0031
0.0032
0.0040
0.0055
0.0055
0.0066
0.0066
0.0033
0.0032
0.0025
0.0026
0.0291
0.0290
0.0005
0.0142
0.0144
0.0172
0.0173
0.0001
0.0028
0.0023
0.0296
0.1977
0.1977
299
Symmetry
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Type
d-d
d-d
MLCT
MLCT
MLCT
MLCT
MLCT
d-d
d-d
MLCT
MLCT
MLCT
MLCT
MLCT
MLCT
MLCT
MLCT
MLCT
MLCT
MLCT
MLCT
MLCT
MLCT
LLCT
LLCT
MLCT
ILCT
ILCT
ILCT
ILCT
ILCT
APPENDIX D (continued)
42
43
44
45
46
47
49
50
4.5780
4.9549
4.9552
5.0196
5.1114
5.1116
5.2032
5.2035
270.83
250.23
250.21
247.00
242.56
242.55
238.28
238.27
0.6547
0.0277
0.0277
0.0303
0.0017
0.0017
0.0056
0.0056
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
ILCT
LLCT
LLCT
ILCT
ILCT
ILCT
MLLCT
MLLCT
Complex 2
Excited State 1: Singlet-?Sym 2.3956 eV 517.54 nm f=0.0006
128 ->141
-0.20308
128 ->142
-0.20060
129 ->141
0.19812
129 ->142
-0.20260
130 ->131
-0.11775
130 ->132
-0.16517
130 ->142
0.52082
This state for optimization and/or second-order correction.
Total Energy, E(RPA) = -1705.50182524
Copying the excited state density for this state as the 1-particle RhoCI density.
Excited state symmetry could not be determined.
Excited State 2: Singlet-?Sym 2.3964 eV 517.37 nm f=0.0006
128 ->141
0.19871
128 ->142
-0.20598
129 ->141
0.20263
129 ->142
0.19895
130 ->131
-0.16613
130 ->132
0.11646
130 ->141
0.51967
Excited state symmetry could not be determined.
Excited State 7: Singlet-?Sym 2.8425 eV 436.18 nm f=0.0217
128 ->131
-0.15997
128 ->132
-0.42763
128 ->142
-0.10701
129 ->131
0.42964
129 ->132
-0.16224
129 ->133
0.14644
129 ->141
0.10927
300
APPENDIX D (continued)
130 ->131
-0.16887
Excited state symmetry could not be determined.
Excited State 8: Singlet-?Sym 2.8428 eV 436.13 nm f=0.0218
128 ->131
0.42839
128 ->132
-0.16203
128 ->133
-0.14555
128 ->141
0.10843
129 ->131
0.15892
129 ->132
0.43010
129 ->142
0.10868
130 ->132
0.16608
Excited state symmetry could not be determined.
Excited State 9: Singlet-?Sym 2.9368 eV 422.17 nm f=0.0001
130 ->133
0.70097
Excited state symmetry could not be determined.
Excited State 10: Singlet-?Sym 3.0535 eV 406.04 nm f=0.0431
128 ->133
0.65062
129 ->133
-0.18546
Excited state symmetry could not be determined.
Excited State 11: Singlet-?Sym 3.0537 eV 406.01 nm f=0.0432
128 ->133
0.18631
129 ->133
0.65035
Excited state symmetry could not be determined.
Excited State 13: Singlet-?Sym 3.2163 eV 385.49 nm f=0.0002
123 ->131
0.14137
123 ->132
-0.16053
123 ->133
0.15499
124 ->131
-0.16184
124 ->132
-0.15106
124 ->133
0.24288
125 ->131
-0.12422
125 ->132
-0.11064
125 ->133
0.16923
126 ->131
-0.11439
126 ->132
0.11640
126 ->133
-0.10615
127 ->131
0.40170
127 ->132
0.14833
301
APPENDIX D (continued)
Excited state symmetry could not be determined.
Excited State 14: Singlet-?Sym 3.2164 eV 385.47 nm f=0.0003
123 ->131
-0.15919
123 ->132
-0.13732
123 ->133
-0.23891
124 ->131
-0.15193
124 ->132
0.16341
124 ->133
0.15481
125 ->131
-0.10305
125 ->132
0.10963
125 ->133
0.10824
126 ->131
0.12120
126 ->132
0.11625
126 ->133
0.18045
127 ->131
-0.14795
127 ->132
0.40420
Excited state symmetry could not be determined.
Excited State 16: Singlet-?Sym 3.2239 eV 384.58 nm f=0.0012
122 ->133
0.34367
123 ->131
-0.16317
123 ->132
-0.17757
124 ->131
0.17175
124 ->132
-0.14144
125 ->131
-0.26834
125 ->132
0.20636
126 ->131
-0.20488
126 ->132
-0.26849
Excited state symmetry could not be determined.
Excited State 17: Singlet-?Sym 3.2307 eV 383.77 nm f=0.0060
122 ->131
-0.28456
122 ->132
-0.24240
123 ->131
-0.14547
123 ->133
0.20160
124 ->132
0.14903
125 ->131
0.10276
125 ->132
-0.23035
126 ->131
-0.21845
126 ->133
0.31185
Excited state symmetry could not be determined.
Excited State 18: Singlet-?Sym 3.2309 eV 383.74 nm f=0.0061
302
APPENDIX D (continued)
122 ->131
122 ->132
123 ->132
124 ->131
124 ->133
125 ->131
125 ->132
125 ->133
126 ->132
-0.24688
0.28298
-0.15116
-0.14138
-0.19507
0.22203
0.10143
0.31949
-0.21899
Excited state symmetry could not be determined.
Excited State 19: Singlet-?Sym 3.5376 eV 350.48 nm f=0.0047
128 ->132
-0.12194
128 ->135
0.14165
128 ->141
-0.23697
128 ->142
0.16145
129 ->131
0.12304
129 ->141
-0.16064
129 ->142
-0.23493
130 ->141
0.37639
Excited state symmetry could not be determined.
Excited State 20: Singlet-?Sym 3.5385 eV 350.38 nm f=0.0047
128 ->131
-0.12123
128 ->141
0.16170
128 ->142
0.23516
129 ->132
-0.12328
129 ->135
-0.14166
129 ->141
-0.23538
129 ->142
0.16252
130 ->142
0.37628
Excited state symmetry could not be determined.
Excited State 22: Singlet-?Sym 3.6753 eV 337.34 nm f=0.0006
125 ->131
0.13829
125 ->132
0.25513
125 ->133
-0.21053
126 ->131
0.25189
126 ->132
-0.13304
126 ->133
0.24022
127 ->131
0.45078
Excited state symmetry could not be determined.
303
APPENDIX D (continued)
Excited State 23: Singlet-?Sym
125 ->131
0.25639
125 ->132
-0.13293
125 ->133
-0.24060
126 ->131
-0.13469
126 ->132
-0.25574
126 ->133
-0.21406
127 ->132
0.44724
3.6759 eV 337.29 nm f=0.0006
Excited state symmetry could not be determined.
Excited State 25: Singlet-?Sym 3.7167 eV 333.59 nm f=0.0001
122 ->133
-0.21664
123 ->131
-0.26155
123 ->132
-0.33000
124 ->131
0.35297
124 ->132
-0.25231
125 ->131
0.14477
125 ->132
-0.12254
126 ->131
0.12278
126 ->132
0.15160
Excited state symmetry could not be determined.
Excited State 26: Singlet-?Sym 3.7250 eV 332.84 nm f=0.0007
122 ->131
0.39681
123 ->131
-0.11089
123 ->132
-0.33633
124 ->131
-0.32013
124 ->133
-0.18467
127 ->132
-0.11671
Excited state symmetry could not be determined.
Excited State 27: Singlet-?Sym 3.7255 eV 332.80 nm f=0.0007
122 ->132
0.40101
123 ->131
-0.31974
123 ->132
0.11723
123 ->133
0.18508
124 ->132
0.32817
127 ->131
0.11579
Excited state symmetry could not be determined.
Excited State 29: Singlet-?Sym 3.7805 eV 327.95 nm f=0.0001
122 ->132
0.10616
123 ->132
-0.10790
304
APPENDIX D (continued)
123 ->133
124 ->133
125 ->131
125 ->132
125 ->133
126 ->131
126 ->132
127 ->131
127 ->132
0.25717
0.47306
0.12008
0.10548
-0.14635
0.11685
-0.13833
-0.25279
-0.11540
Excited state symmetry could not be determined.
Excited State 30: Singlet-?Sym 3.7812 eV 327.90 nm f=0.0001
123 ->133
0.47672
124 ->132
-0.11164
124 ->133
-0.26259
125 ->131
-0.11080
125 ->132
0.13591
126 ->131
0.12564
126 ->132
0.12124
126 ->133
0.13874
127 ->131
-0.11452
127 ->132
0.25422
Excited state symmetry could not be determined.
Excited State 31: Singlet-?Sym 3.7887 eV 327.25 nm f=0.0001
122 ->131
0.35137
122 ->132
0.16953
123 ->131
0.13932
123 ->133
-0.12242
124 ->132
-0.13360
125 ->131
0.10188
125 ->132
-0.13628
125 ->133
0.18950
126 ->131
-0.14890
126 ->132
-0.12358
126 ->133
0.40589
Excited state symmetry could not be determined.
Excited State 32: Singlet-?Sym 3.7895 eV 327.18 nm f=0.0001
122 ->131
0.17455
122 ->132
-0.34956
123 ->132
0.13410
124 ->131
0.12893
305
APPENDIX D (continued)
124 ->133
125 ->131
125 ->132
125 ->133
126 ->131
126 ->132
126 ->133
0.13366
0.15093
0.10893
0.40421
0.12496
-0.12930
-0.18186
Excited state symmetry could not be determined.
Excited State 33: Singlet-?Sym 3.7994 eV 326.32 nm f=0.0003
122 ->133
0.56081
125 ->131
0.23028
125 ->132
-0.19819
126 ->131
0.17843
126 ->132
0.22939
Excited state symmetry could not be determined.
Excited State 34: Singlet-?Sym 3.8430 eV 322.62 nm f=0.0013
120 ->131
-0.11682
121 ->132
0.11621
130 ->134
0.66912
Excited state symmetry could not be determined.
Excited State 35: Singlet-?Sym 3.8803 eV 319.52 nm f=0.0005
119 ->131
0.12929
120 ->132
0.10119
121 ->131
-0.10037
128 ->135
0.50972
129 ->134
-0.12342
129 ->135
-0.32362
Excited state symmetry could not be determined.
Excited State 36: Singlet-?Sym 3.8806 eV 319.50 nm f=0.0005
119 ->132
-0.12889
120 ->131
-0.10116
121 ->132
-0.10006
128 ->134
0.12401
128 ->135
0.32274
129 ->135
0.50927
Excited state symmetry could not be determined.
Excited State 37: Singlet-?Sym 3.9063 eV 317.39 nm f=0.0012
124 ->135
0.17092
306
APPENDIX D (continued)
126 ->134
127 ->136
128 ->134
129 ->135
0.21676
-0.10846
0.51287
-0.13609
Excited state symmetry could not be determined.
Excited State 38: Singlet-?Sym 3.9067 eV 317.37 nm f=0.0013
123 ->135
0.16975
125 ->134
0.21535
127 ->137
0.10790
128 ->135
0.13600
129 ->134
0.51489
Excited state symmetry could not be determined.
Excited State 40: Singlet-?Sym 3.9398 eV 314.69 nm f=0.0032
122 ->134
0.26374
124 ->134
-0.20423
124 ->136
0.14436
124 ->138
0.15563
124 ->139
-0.11005
126 ->135
-0.15685
126 ->136
-0.10299
126 ->137
0.16616
126 ->138
-0.12126
126 ->139
-0.16992
127 ->135
-0.21650
127 ->139
-0.13655
128 ->137
0.10006
Excited state symmetry could not be determined.
Excited State 41: Singlet-?Sym 3.9404 eV 314.65 nm f=0.0017
122 ->134
0.18844
122 ->136
0.14549
123 ->134
0.10960
123 ->136
0.11451
123 ->139
-0.14594
124 ->134
0.25787
125 ->137
0.12818
125 ->138
-0.15846
126 ->135
0.21177
126 ->138
-0.11676
127 ->135
-0.15055
127 ->137
-0.10771
307
APPENDIX D (continued)
127 ->138
128 ->135
129 ->137
0.16970
-0.11877
0.10467
Excited state symmetry could not be determined.
Excited State 42: Singlet-?Sym 3.9406 eV 314.63 nm f=0.0010
122 ->134
-0.14543
122 ->137
-0.15145
123 ->134
0.29876
123 ->137
0.13669
123 ->138
0.14572
125 ->135
0.24095
125 ->136
-0.16487
125 ->139
-0.16238
127 ->135
0.11429
127 ->136
-0.10955
127 ->138
0.12629
127 ->139
-0.15526
129 ->135
-0.13938
129 ->136
-0.11458
Excited state symmetry could not be determined.
Excited State 43: Singlet-?Sym 3.9624 eV 312.90 nm f=0.0090
122 ->139
0.13801
123 ->134
-0.10783
124 ->135
-0.19020
125 ->139
0.10254
126 ->134
-0.29828
127 ->136
0.13496
128 ->134
0.42007
Excited state symmetry could not be determined.
Excited State 44: Singlet-?Sym 3.9626 eV 312.89 nm f=0.0089
122 ->138
0.14083
123 ->135
-0.19122
124 ->134
0.10588
125 ->134
-0.29962
125 ->138
-0.10111
126 ->139
0.10112
127 ->137
-0.13441
129 ->134
0.41829
Excited state symmetry could not be determined.
308
APPENDIX D (continued)
Excited State 46: Singlet-?Sym
120 ->131
-0.20138
120 ->132
0.18453
121 ->131
-0.18705
121 ->132
-0.20114
130 ->136
0.49450
130 ->137
0.10554
130 ->138
0.10419
130 ->139
-0.15543
4.0157 eV 308.75 nm f=0.0012
Excited state symmetry could not be determined.
Excited State 47: Singlet-?Sym 4.0161 eV 308.72 nm f=0.0012
120 ->131
0.19116
120 ->132
0.19515
121 ->131
-0.20947
121 ->132
0.18246
130 ->136
-0.10534
130 ->137
0.49193
130 ->138
0.15690
130 ->139
0.10448
Excited state symmetry could not be determined.
Excited State 48: Singlet-?Sym 4.0235 eV 308.15 nm f=0.0337
120 ->131
-0.25811
120 ->132
-0.13018
121 ->131
-0.13302
121 ->132
0.25874
128 ->136
-0.18362
128 ->137
0.32559
129 ->136
0.32604
129 ->137
0.18304
130 ->134
-0.15914
Excited state symmetry could not be determined.
Excited State 50: Singlet-?Sym 4.0535 eV 305.87 nm f=0.0517
119 ->132
-0.14172
120 ->131
0.31929
120 ->132
-0.12361
121 ->131
0.11883
121 ->132
0.31868
121 ->133
-0.14392
130 ->136
0.43097
309
APPENDIX D (continued)
Excited state symmetry could not be determined.
Excited State 51: Singlet-?Sym 4.0537 eV 305.85 nm f=0.0511
119 ->131
0.14666
120 ->131
-0.11867
120 ->132
-0.32304
120 ->133
-0.14252
121 ->131
0.31323
121 ->132
-0.12177
130 ->137
0.43239
Excited state symmetry could not be determined.
Excited State 52: Singlet-?Sym 4.0739 eV 304.34 nm f=0.0280
119 ->131
-0.13552
119 ->132
0.14936
121 ->133
0.32139
128 ->135
0.12201
128 ->136
0.28389
129 ->137
0.28537
130 ->136
0.15418
130 ->138
-0.16947
130 ->139
0.24421
Excited state symmetry could not be determined.
Excited State 53: Singlet-?Sym 4.0742 eV 304.32 nm f=0.0281
119 ->131
-0.15356
119 ->132
-0.13369
120 ->133
0.31828
128 ->137
-0.28457
129 ->135
-0.12164
129 ->136
0.28407
130 ->137
0.15649
130 ->138
-0.24597
130 ->139
-0.16892
Excited state symmetry could not be determined.
Excited State 54: Singlet-?Sym 4.0947 eV 302.79 nm f=0.0018
119 ->131
0.52593
120 ->133
0.42534
121 ->133
0.16161
Excited state symmetry could not be determined.
Excited State 55: Singlet-?Sym 4.0951 eV 302.77 nm f=0.0017
119 ->132
0.52870
310
APPENDIX D (continued)
120 ->133
121 ->133
0.16203
-0.42064
Excited state symmetry could not be determined.
Excited State 56: Singlet-?Sym 4.1172 eV 301.14 nm f=0.0060
119 ->133
0.53497
120 ->131
0.22324
120 ->132
0.11464
121 ->131
0.11436
121 ->132
-0.22495
128 ->137
0.17159
129 ->136
0.17183
Excited state symmetry could not be determined.
Excited State 57: Singlet-?Sym 4.1320 eV 300.06 nm f=0.0021
119 ->131
0.13582
128 ->136
0.14733
128 ->137
-0.30505
129 ->136
0.30766
129 ->137
0.14017
130 ->138
0.45589
Excited state symmetry could not be determined.
Excited State 58: Singlet-?Sym 4.1322 eV 300.05 nm f=0.0020
119 ->132
0.13826
128 ->136
-0.30593
128 ->137
-0.14537
129 ->136
0.14221
129 ->137
-0.30438
130 ->139
0.45683
Excited state symmetry could not be determined.
Excited State 60: Singlet-?Sym 4.2041 eV 294.91 nm f=0.0122
119 ->133
-0.13104
128 ->138
0.30076
128 ->139
0.36934
129 ->138
0.37068
129 ->139
-0.29737
Excited state symmetry could not be determined.
Excited State 61: Singlet-?Sym 4.2230 eV 293.59 nm f=0.0036
121 ->133
0.10475
128 ->138
0.32905
311
APPENDIX D (continued)
128 ->139
129 ->138
129 ->139
130 ->139
-0.27111
0.26845
0.33101
-0.25574
Excited state symmetry could not be determined.
Excited State 62: Singlet-?Sym 4.2231 eV 293.58 nm f=0.0036
120 ->133
0.10420
128 ->138
-0.27002
128 ->139
-0.32972
129 ->138
0.33180
129 ->139
-0.27066
130 ->138
0.25351
Excited state symmetry could not be determined.
Excited State 63: Singlet-?Sym 4.3415 eV 285.58 nm f=0.1625
119 ->131
-0.26902
120 ->132
-0.14695
120 ->133
0.27996
120 ->134
-0.10476
121 ->131
0.14547
128 ->138
0.16650
128 ->139
0.13336
129 ->138
-0.13279
129 ->139
0.16547
130 ->138
0.27761
Excited state symmetry could not be determined.
Excited State 64: Singlet-?Sym 4.3418 eV 285.56 nm f=0.1626
119 ->132
0.26862
120 ->131
0.14630
121 ->132
0.14459
121 ->133
0.28146
121 ->134
-0.10466
128 ->138
-0.13417
128 ->139
0.16733
129 ->138
-0.16558
129 ->139
-0.13396
130 ->139
-0.27625
Excited state symmetry could not be determined.
Excited State 66: Singlet-?Sym 4.4506 eV 278.58 nm f=0.5713
119 ->133
0.38545
312
APPENDIX D (continued)
120 ->131
121 ->132
122 ->134
128 ->136
128 ->137
129 ->136
129 ->137
130 ->134
-0.19406
0.19430
0.10798
0.11169
-0.20014
-0.20001
-0.11185
-0.11076
Excited state symmetry could not be determined.
Excited State 68: Singlet-?Sym 4.5161 eV 274.54 nm f=0.0012
124 ->135
-0.33058
125 ->136
-0.16066
126 ->134
0.44775
126 ->137
0.16138
127 ->136
0.25777
Excited state symmetry could not be determined.
Excited State 69: Singlet-?Sym 4.5165 eV 274.51 nm f=0.0012
123 ->135
-0.32856
125 ->134
0.44775
125 ->137
-0.17132
126 ->136
-0.15044
127 ->137
-0.25745
Excited state symmetry could not be determined.
Excited State 70: Singlet-?Sym 4.5251 eV 273.99 nm f=0.0214
122 ->134
0.39271
123 ->137
0.12929
124 ->136
-0.17141
126 ->138
-0.12196
126 ->139
-0.10638
127 ->135
0.44611
Excited state symmetry could not be determined.
Excited State 72: Singlet-?Sym 4.5272 eV 273.86 nm f=0.0006
122 ->137
-0.18723
123 ->134
-0.40118
123 ->137
0.15486
124 ->136
0.10877
125 ->135
0.40348
125 ->139
0.10853
127 ->139
0.11684
313
APPENDIX D (continued)
Excited state symmetry could not be determined.
Excited State 73: Singlet-?Sym 4.6873 eV 264.51 nm f=0.0002
122 ->134
-0.23321
123 ->137
-0.17921
124 ->136
0.16441
125 ->136
0.29477
125 ->137
0.10332
126 ->136
-0.13126
126 ->137
0.27840
127 ->135
0.40576
Excited state symmetry could not be determined.
Excited State 76: Singlet-?Sym 4.7121 eV 263.12 nm f=0.0005
122 ->137
-0.16074
123 ->134
-0.10246
123 ->138
0.14724
124 ->135
0.47777
124 ->136
-0.10275
124 ->139
-0.15271
125 ->136
-0.10908
126 ->134
0.21392
127 ->136
0.15247
127 ->138
0.14309
127 ->139
-0.18467
Excited state symmetry could not be determined.
Excited State 77: Singlet-?Sym 4.7125 eV 263.10 nm f=0.0005
122 ->136
-0.16794
123 ->135
0.47897
123 ->139
0.14772
124 ->134
0.10366
124 ->138
0.14901
125 ->134
0.21257
125 ->137
-0.10749
126 ->136
-0.11031
127 ->137
-0.14473
127 ->138
-0.18178
127 ->139
-0.14274
Excited state symmetry could not be determined.
Excited State 82: Singlet-?Sym 4.7409 eV 261.52 nm f=0.0003
122 ->139
0.29592
123 ->134
0.12384
314
APPENDIX D (continued)
124 ->134
125 ->134
125 ->137
125 ->138
125 ->139
126 ->134
126 ->138
126 ->139
127 ->137
0.18085
-0.17909
-0.10278
0.26524
0.23305
0.11445
0.15679
-0.20887
-0.24905
Excited state symmetry could not be determined.
Excited State 83: Singlet-?Sym 4.7412 eV 261.50 nm f=0.0003
122 ->138
0.30431
123 ->134
0.18702
124 ->134
-0.12767
125 ->134
0.11824
125 ->138
-0.19138
125 ->139
0.24921
126 ->134
0.17742
126 ->138
0.22885
126 ->139
0.20829
127 ->136
-0.25161
Excited state symmetry could not be determined.
Excited State 84: Singlet-?Sym 4.7490 eV 261.08 nm f=0.0096
122 ->134
0.34430
123 ->138
0.16637
123 ->139
0.16183
124 ->138
-0.16531
124 ->139
0.15778
125 ->136
0.17074
125 ->138
0.22076
125 ->139
-0.22092
126 ->137
0.16962
126 ->138
0.22771
126 ->139
0.21347
Excited state symmetry could not be determined.
Excited State 85: Singlet-?Sym 4.8131 eV 257.60 nm f=0.0003
122 ->138
0.19125
123 ->137
0.35997
124 ->136
0.40273
127 ->136
0.34708
315
APPENDIX D (continued)
Excited state symmetry could not be determined.
Excited State 86: Singlet-?Sym 4.8137 eV 257.57 nm f=0.0002
122 ->139
0.19225
123 ->136
0.39136
124 ->137
-0.37273
127 ->137
0.34611
Excited state symmetry could not be determined.
Excited State 87: Singlet-?Sym 4.8208 eV 257.19 nm f=0.0020
123 ->136
0.26909
123 ->137
-0.26205
123 ->138
0.14004
124 ->136
0.23589
124 ->137
0.29523
124 ->139
0.14008
125 ->136
-0.26827
126 ->137
-0.25857
127 ->135
0.10110
Excited state symmetry could not be determined.
Excited State 88: Singlet-?Sym 4.8213 eV 257.16 nm f=0.0005
123 ->136
-0.19538
123 ->137
-0.30925
123 ->139
0.13840
124 ->136
0.26336
124 ->137
-0.20880
124 ->138
-0.15395
125 ->137
-0.28703
126 ->136
0.30994
Excited state symmetry could not be determined.
Excited State 89: Singlet-?Sym 4.8314 eV 256.62 nm f=0.0001
122 ->136
0.52196
123 ->138
-0.10371
123 ->139
0.15739
124 ->138
0.14387
124 ->139
0.10169
125 ->137
-0.24878
126 ->136
-0.22733
127 ->138
0.11158
Excited state symmetry could not be determined.
Excited State 90: Singlet-?Sym 4.8320 eV 256.59 nm f=0.0001
316
APPENDIX D (continued)
122 ->137
123 ->138
123 ->139
124 ->139
125 ->136
126 ->137
127 ->139
0.52410
0.14942
0.10555
-0.15356
-0.23496
0.23706
0.11204
Excited state symmetry could not be determined.
Excited State 94: Singlet-?Sym 4.9105 eV 252.49 nm f=0.0010
123 ->138
0.24089
123 ->139
0.27653
124 ->138
-0.27156
124 ->139
0.26837
125 ->138
-0.18987
125 ->139
0.20319
126 ->137
0.10478
126 ->138
-0.21599
126 ->139
-0.20105
127 ->135
-0.10249
Excited state symmetry could not be determined.
Excited State 97: Singlet-?Sym 4.9364 eV 251.16 nm f=0.0349
120 ->135
-0.13136
121 ->134
0.62745
Excited state symmetry could not be determined.
Excited State 98: Singlet-?Sym 4.9369 eV 251.14 nm f=0.0348
120 ->134
0.62819
121 ->135
0.12916
Excited state symmetry could not be determined.
Excited State 99: Singlet-?Sym 4.9690 eV 249.52 nm f=0.0163
120 ->134
-0.13322
121 ->135
0.65659
Excited state symmetry could not be determined.
Excited State 100: Singlet-?Sym 4.9692 eV 249.51 nm f=0.0163
120 ->135
0.65599
121 ->134
0.13517
317
APPENDIX D (continued)
No.
1
2
7
8
9
10
11
13
14
16
17
18
19
20
22
23
25
26
27
29
30
31
32
33
34
35
36
37
38
40
41
42
43
44
46
47
48
50
51
52
Energy
(eV)
2.3956
2.3964
2.8425
2.8428
2.9368
3.0535
3.0537
3.2163
3.2164
3.2239
3.2307
3.2309
3.5376
3.5385
3.6753
3.6759
3.7167
3.7250
3.7255
3.7805
3.7812
3.7887
3.7895
3.7994
3.8430
3.8803
3.8806
3.9063
3.9067
3.9398
3.9404
3.9406
3.9624
3.9626
4.0157
4.0161
4.0235
4.0535
4.0537
4.0739
Wavelength(nm)
517.54
517.37
436.18
436.13
422.17
406.04
406.01
385.49
385.47
384.58
383.77
383.74
350.48
350.38
337.34
337.29
333.59
332.84
332.80
327.95
327.90
327.25
327.18
326.32
322.62
319.52
319.50
317.39
317.37
314.69
314.65
314.63
312.90
312.89
308.75
308.72
308.15
305.87
305.85
304.34
f
0.0006
0.0006
0.0217
0.0218
0.0001
0.0431
0.0432
0.0002
0.0003
0.0012
0.0060
0.0061
0.0047
0.0047
0.0006
0.0006
0.0001
0.0007
0.0007
0.0001
0.0001
0.0001
0.0001
0.0003
0.0013
0.0005
0.0005
0.0012
0.0013
0.0032
0.0017
0.0010
0.0090
0.0089
0.0012
0.0012
0.0337
0.0517
0.0511
0.0280
318
Symmetry
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Type
MLCT/d-d
MLCT/d-d
MLCT
MLCT
MLCT
MLCT
MLCT
ILCT
ILCT
ILCT
ILCT
ILCT
MLCT/d-d
MLCT/d-d
LLCT
LLCT
ILCT
ILCT
LLCT
ILCT
ILCT
ILCT
ILCT
ILCT
MLCT
MLCT
MLCT
MLCT
MLCT
ILCT
ILCT
ILCT
MLCT
MLCT
MLCT
MLCT
MLCT
MLLCT
MLLCT
MLLCT
APPENDIX D (continued)
53
54
55
56
57
58
60
61
62
63
64
66
68
69
70
72
73
76
77
82
83
84
85
86
87
88
89
90
94
97
98
99
100
4.0742
4.0947
4.0951
4.1172
4.1320
4.1322
4.2041
4.2230
4.2231
4.3415
4.3418
4.4506
4.5161
4.5165
4.5251
4.5272
4.6873
4.7121
4.7125
4.7409
4.7412
4.7490
4.8131
4.8137
4.8208
4.8213
4.8314
4.8320
4.9105
4.9364
4.9369
4.9690
4.9692
304.32
302.79
302.77
301.14
300.06
300.05
294.91
293.59
293.58
285.58
285.56
278.58
274.54
274.51
273.99
273.86
264.51
263.12
263.10
261.52
261.50
261.08
257.60
257.57
257.19
257.16
256.62
256.59
252.49
251.16
251.14
249.52
249.51
0.0281
0.0018
0.0017
0.0060
0.0021
0.0020
0.0122
0.0036
0.0036
0.1625
0.1626
0.5713
0.0012
0.0012
0.0214
0.0006
0.0002
0.0005
0.0005
0.0003
0.0003
0.0096
0.0003
0.0002
0.0020
0.0005
0.0001
0.0001
0.0010
0.0349
0.0348
0.0163
0.0163
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Complex 3
Excited State 1: Singlet-?Sym
146 ->161
-0.21355
146 ->162
0.16312
147 ->161
-0.17546
147 ->162
-0.33966
148 ->161
0.45074
2.3379 eV 530.33 nm f=0.0002
319
MLLCT
LLCT
LLCT
MLLCT
mlct
MLCT
MLCT
MLCT
MLLCT
MLLCT
MLLCT
MLLCT
ILCT
ILCT
ILCT
ILCT
ILCT
ILCT
ILCT
ILCT
ILCT
ILCT
LLCT
LLCT
ILCT
ILCT
LLCT
LLCT
ILCT
LLCT
LLCT
LLCT
LLCT
APPENDIX D (continued)
148 ->162
0.25645
This state for optimization and/or second-order correction.
Total Energy, E(RPA) = -1838.13456293
Copying the excited state density for this state as the 1-particle RhoCI density.
Excited state symmetry could not be determined.
Excited State 2: Singlet-?Sym 2.3389 eV 530.09 nm f=0.0003
146 ->162
-0.36726
147 ->161
0.24205
148 ->161
0.38167
148 ->162
-0.37890
Excited state symmetry could not be determined.
Excited State 4: Singlet-?Sym 2.7349 eV 453.34 nm f=0.0015
146 ->161
-0.15041
147 ->149
-0.16695
147 ->150
-0.10731
147 ->162
-0.14236
148 ->149
0.49577
148 ->150
-0.39475
Excited state symmetry could not be determined.
Excited State 5: Singlet-?Sym 2.7365 eV 453.08 nm f=0.0013
146 ->149
0.15651
146 ->150
0.25183
146 ->162
0.13458
147 ->149
-0.21239
147 ->161
-0.14414
148 ->149
0.31431
148 ->150
0.46505
Excited state symmetry could not be determined.
Excited State 6: Singlet-?Sym 2.7872 eV 444.83 nm f=0.0002
146 ->149
-0.32611
146 ->150
0.32787
147 ->149
0.33794
147 ->150
0.34380
148 ->149
0.10935
Excited state symmetry could not be determined.
Excited State 7: Singlet-?Sym 2.8342 eV 437.46 nm f=0.0238
146 ->150
0.37811
147 ->149
-0.36962
320
APPENDIX D (continued)
147 ->150
147 ->151
148 ->149
148 ->150
0.15703
0.11471
-0.30270
-0.23970
Excited state symmetry could not be determined.
Excited State 8: Singlet-?Sym 2.8355 eV 437.26 nm f=0.0240
146 ->149
0.44207
146 ->150
-0.15807
146 ->151
0.11911
147 ->150
0.43464
148 ->149
0.12933
148 ->150
-0.14473
Excited state symmetry could not be determined.
Excited State 9: Singlet-?Sym 2.9495 eV 420.35 nm f=0.0002
146 ->151
0.11716
148 ->151
0.68461
Excited state symmetry could not be determined.
Excited State 11: Singlet-?Sym 3.0136 eV 411.42 nm f=0.0403
146 ->152
0.11683
147 ->151
0.66744
Excited state symmetry could not be determined.
Excited State 12: Singlet-?Sym 3.0143 eV 411.32 nm f=0.0394
146 ->151
0.66436
147 ->152
-0.12063
148 ->151
-0.10722
Excited state symmetry could not be determined.
Excited State 13: Singlet-?Sym 3.1398 eV 394.88 nm f=0.0328
147 ->152
0.64916
148 ->152
0.10991
Excited state symmetry could not be determined.
Excited State 14: Singlet-?Sym 3.1412 eV 394.70 nm f=0.0321
146 ->152
0.64955
147 ->152
0.10214
Excited state symmetry could not be determined.
Excited State 15: Singlet-?Sym 3.2863 eV 377.28 nm f=0.0236
147 ->153
0.11062
321
APPENDIX D (continued)
148 ->153
148 ->154
-0.31924
0.59323
Excited state symmetry could not be determined.
Excited State 16: Singlet-?Sym 3.2871 eV 377.18 nm f=0.0246
146 ->153
0.16877
146 ->154
0.14767
147 ->153
-0.15330
148 ->153
0.54639
148 ->154
0.30936
Excited state symmetry could not be determined.
Excited State 17: Singlet-?Sym 3.2930 eV 376.51 nm f=0.0001
146 ->153
-0.20365
146 ->154
0.40624
147 ->153
0.43269
147 ->154
0.21547
148 ->152
0.17850
Excited state symmetry could not be determined.
Excited State 18: Singlet-?Sym 3.3315 eV 372.15 nm f=0.0059
146 ->153
0.22899
146 ->154
0.36968
147 ->153
-0.34809
147 ->154
0.29073
148 ->153
-0.25521
Excited state symmetry could not be determined.
Excited State 19: Singlet-?Sym 3.3322 eV 372.08 nm f=0.0070
146 ->153
0.38861
146 ->154
-0.29816
147 ->153
0.25644
147 ->154
0.39422
Excited state symmetry could not be determined.
Excited State 20: Singlet-?Sym 3.3553 eV 369.52 nm f=0.0241
146 ->153
0.43139
146 ->154
0.21110
147 ->153
0.21483
147 ->154
-0.41870
Excited state symmetry could not be determined.
Excited State 22: Singlet-?Sym 3.5100 eV 353.23 nm f=0.0024
322
APPENDIX D (continued)
146 ->150
146 ->161
146 ->162
147 ->149
147 ->161
148 ->162
0.13974
0.14712
-0.18574
-0.13720
0.25242
0.43054
Excited state symmetry could not be determined.
Excited State 23: Singlet-?Sym 3.5107 eV 353.16 nm f=0.0024
146 ->149
-0.11600
146 ->161
0.32177
146 ->162
0.12029
147 ->150
-0.11506
147 ->161
-0.18624
147 ->162
0.26919
148 ->150
-0.10127
148 ->161
0.29909
Excited state symmetry could not be determined.
Excited State 25: Singlet-?Sym 3.9406 eV 314.63 nm f=0.0146
141 ->152
0.10989
143 ->149
0.17379
143 ->150
0.21375
143 ->151
-0.22671
144 ->149
0.23640
144 ->150
-0.17651
144 ->151
0.20297
145 ->149
0.34704
145 ->150
-0.12553
Excited state symmetry could not be determined.
Excited State 26: Singlet-?Sym 3.9408 eV 314.62 nm f=0.0146
141 ->152
0.10018
142 ->152
0.10919
143 ->149
0.26350
143 ->150
-0.10814
143 ->151
-0.20056
144 ->149
-0.16014
144 ->150
-0.23943
144 ->151
-0.23512
145 ->150
0.36277
Excited state symmetry could not be determined.
323
APPENDIX D (continued)
Excited State 27: Singlet-?Sym
140 ->152
-0.13497
141 ->153
-0.12629
142 ->154
-0.12085
143 ->149
0.37080
143 ->150
0.19921
144 ->149
-0.16169
144 ->150
0.36661
145 ->151
-0.26953
3.9431 eV 314.43 nm f=0.0001
Excited state symmetry could not be determined.
Excited State 28: Singlet-?Sym 4.0616 eV 305.26 nm f=0.0016
143 ->149
0.20561
143 ->150
-0.41172
144 ->149
0.43347
144 ->150
0.21142
145 ->152
-0.14975
Excited state symmetry could not be determined.
Excited State 29: Singlet-?Sym 4.0926 eV 302.95 nm f=0.0003
143 ->149
-0.28283
143 ->151
-0.11510
144 ->149
-0.11513
144 ->150
0.32311
144 ->152
-0.13447
145 ->149
0.43805
145 ->150
0.21499
Excited state symmetry could not be determined.
Excited State 30: Singlet-?Sym 4.0936 eV 302.87 nm f=0.0003
143 ->149
-0.12731
143 ->150
0.38914
143 ->152
0.13223
144 ->149
0.33274
144 ->151
-0.12902
145 ->149
-0.16531
145 ->150
0.35529
Excited state symmetry could not be determined.
Excited State 31: Singlet-?Sym 4.1132 eV 301.43 nm f=0.0017
143 ->152
0.14842
144 ->149
-0.13329
144 ->151
0.54707
324
APPENDIX D (continued)
145 ->149
145 ->150
-0.18878
0.29117
Excited state symmetry could not be determined.
Excited State 32: Singlet-?Sym 4.1142 eV 301.35 nm f=0.0018
143 ->149
0.15915
143 ->151
0.55096
144 ->150
-0.15424
144 ->152
-0.14338
145 ->149
0.24688
145 ->150
0.17217
Excited state symmetry could not be determined.
Excited State 34: Singlet-?Sym 4.1707 eV 297.28 nm f=0.0014
140 ->150
0.11656
141 ->149
-0.11589
141 ->151
0.12124
142 ->150
0.11364
143 ->152
0.46996
143 ->153
-0.10521
144 ->151
-0.12353
144 ->152
0.28331
145 ->149
0.13306
Excited state symmetry could not be determined.
Excited State 35: Singlet-?Sym 4.1709 eV 297.26 nm f=0.0014
140 ->149
-0.11642
141 ->150
0.11607
142 ->149
0.11256
142 ->151
0.12331
143 ->151
0.12046
143 ->152
-0.27969
144 ->152
0.47254
145 ->150
0.13515
Excited state symmetry could not be determined.
Excited State 36: Singlet-?Sym 4.1978 eV 295.35 nm f=0.0155
140 ->151
-0.15160
141 ->149
-0.18483
142 ->150
-0.18452
143 ->150
-0.11437
143 ->153
-0.15402
144 ->149
0.11399
325
APPENDIX D (continued)
144 ->154
145 ->152
148 ->155
-0.15557
0.51288
0.12254
Excited state symmetry could not be determined.
Excited State 38: Singlet-?Sym 4.2727 eV 290.18 nm f=0.0079
144 ->151
0.11858
147 ->155
0.67098
Excited state symmetry could not be determined.
Excited State 39: Singlet-?Sym 4.2739 eV 290.10 nm f=0.0080
143 ->151
-0.11739
146 ->155
0.67009
Excited state symmetry could not be determined.
Excited State 40: Singlet-?Sym 4.3052 eV 287.99 nm f=0.0016
142 ->150
0.12344
143 ->153
0.27426
144 ->153
-0.11600
144 ->154
0.45401
145 ->152
0.34678
145 ->153
-0.13915
Excited state symmetry could not be determined.
Excited State 41: Singlet-?Sym 4.3072 eV 287.85 nm f=0.0086
140 ->150
-0.11511
141 ->150
-0.13390
142 ->149
-0.10564
142 ->151
-0.14282
143 ->153
-0.10509
143 ->154
-0.26801
144 ->152
0.31590
144 ->153
-0.28057
144 ->154
-0.10651
145 ->154
0.36120
Excited state symmetry could not be determined.
Excited State 42: Singlet-?Sym 4.3084 eV 287.78 nm f=0.0083
140 ->149
-0.11109
141 ->149
0.15046
141 ->151
-0.13888
143 ->152
0.31826
143 ->153
0.43436
326
APPENDIX D (continued)
144 ->154
145 ->153
-0.18640
0.27802
Excited state symmetry could not be determined.
Excited State 43: Singlet-?Sym 4.3835 eV 282.84 nm f=0.0091
143 ->153
-0.26931
144 ->151
0.10157
144 ->154
0.32957
145 ->153
0.51465
145 ->154
0.10577
Excited state symmetry could not be determined.
Excited State 44: Singlet-?Sym 4.3845 eV 282.78 nm f=0.0089
143 ->154
0.29625
144 ->153
0.40784
145 ->154
0.44058
Excited state symmetry could not be determined.
Excited State 45: Singlet-?Sym 4.3885 eV 282.52 nm f=0.0003
143 ->154
0.53836
144 ->153
-0.41923
Excited state symmetry could not be determined.
Excited State 46: Singlet-?Sym 4.4589 eV 278.06 nm f=0.0039
141 ->149
-0.19333
142 ->150
0.19017
145 ->153
0.15224
148 ->156
0.18056
148 ->157
0.58141
Excited state symmetry could not be determined.
Excited State 47: Singlet-?Sym 4.4596 eV 278.02 nm f=0.0044
141 ->150
-0.18742
142 ->149
-0.20541
145 ->154
-0.15763
146 ->156
0.16491
147 ->156
-0.11444
147 ->157
0.10196
148 ->156
0.54440
148 ->157
-0.16919
Excited state symmetry could not be determined.
Excited State 48: Singlet-?Sym 4.4695 eV 277.40 nm f=0.0001
327
APPENDIX D (continued)
141 ->149
141 ->150
142 ->149
142 ->150
0.21790
-0.41820
0.44841
0.23060
Excited state symmetry could not be determined.
Excited State 49: Singlet-?Sym 4.4794 eV 276.79 nm f=0.0232
140 ->150
0.14344
141 ->149
0.31350
141 ->150
-0.11603
141 ->151
0.32949
142 ->150
-0.30261
142 ->151
0.20612
146 ->157
-0.12041
147 ->156
0.15166
148 ->157
0.18631
Excited state symmetry could not be determined.
Excited State 50: Singlet-?Sym 4.4797 eV 276.77 nm f=0.0221
140 ->149
-0.14383
141 ->150
-0.32504
141 ->151
-0.20597
142 ->149
-0.28841
142 ->150
0.11572
142 ->151
0.33187
146 ->156
-0.16953
147 ->157
-0.15115
148 ->156
-0.14300
Excited state symmetry could not be determined.
Excited State 51: Singlet-?Sym 4.5045 eV 275.24 nm f=0.0046
146 ->156
-0.47166
147 ->157
0.48095
Excited state symmetry could not be determined.
Excited State 52: Singlet-?Sym 4.5164 eV 274.52 nm f=0.0085
140 ->149
0.17627
140 ->150
-0.20239
141 ->152
0.14794
142 ->151
0.27133
146 ->156
0.32384
146 ->157
0.13232
147 ->156
-0.10672
328
APPENDIX D (continued)
147 ->157
148 ->156
0.33496
-0.19840
Excited state symmetry could not be determined.
Excited State 53: Singlet-?Sym 4.5172 eV 274.47 nm f=0.0082
140 ->149
-0.21178
140 ->150
-0.17930
141 ->151
0.29086
142 ->152
-0.14462
146 ->156
-0.12772
146 ->157
0.35316
147 ->156
-0.34180
147 ->157
-0.12626
Excited state symmetry could not be determined.
Excited State 54: Singlet-?Sym 4.5359 eV 273.34 nm f=0.0163
140 ->149
-0.24529
140 ->151
0.44583
141 ->149
-0.29105
141 ->150
-0.16725
141 ->151
0.13557
142 ->150
-0.18423
146 ->156
0.10998
Excited state symmetry could not be determined.
Excited State 55: Singlet-?Sym 4.5371 eV 273.26 nm f=0.0031
140 ->149
-0.29970
140 ->150
0.32959
140 ->151
-0.19567
142 ->149
-0.16481
142 ->150
0.10294
142 ->151
-0.27990
146 ->156
0.13793
147 ->157
0.19043
148 ->156
-0.21426
Excited state symmetry could not be determined.
Excited State 56: Singlet-?Sym 4.5374 eV 273.25 nm f=0.0031
140 ->149
0.26838
140 ->150
0.34340
140 ->151
0.19919
141 ->151
-0.25951
142 ->150
-0.21553
329
APPENDIX D (continued)
142 ->151
146 ->157
147 ->156
148 ->157
-0.11603
0.22450
-0.20083
0.14325
Excited state symmetry could not be determined.
Excited State 57: Singlet-?Sym 4.6061 eV 269.17 nm f=0.0441
142 ->152
0.62800
144 ->155
-0.10357
146 ->157
0.10441
147 ->156
-0.11899
Excited state symmetry could not be determined.
Excited State 58: Singlet-?Sym 4.6065 eV 269.15 nm f=0.0452
141 ->152
0.62650
143 ->155
-0.10470
146 ->156
-0.11364
147 ->157
-0.11603
Excited state symmetry could not be determined.
Excited State 60: Singlet-?Sym 4.7036 eV 263.59 nm f=0.0001
140 ->152
0.59158
141 ->153
-0.19220
142 ->154
-0.20114
146 ->157
0.15960
147 ->156
0.15701
Excited state symmetry could not be determined.
Excited State 61: Singlet-?Sym 4.7240 eV 262.46 nm f=0.0688
140 ->154
0.11096
141 ->151
-0.12772
141 ->154
0.41860
142 ->153
0.42809
144 ->155
-0.14905
145 ->156
-0.10753
Excited state symmetry could not be determined.
Excited State 62: Singlet-?Sym 4.7241 eV 262.45 nm f=0.0690
140 ->153
0.11069
141 ->153
-0.42219
142 ->151
0.13134
142 ->154
0.42519
143 ->155
-0.14656
330
APPENDIX D (continued)
Excited state symmetry could not be determined.
Excited State 64: Singlet-?Sym 4.7559 eV 260.70 nm f=0.0027
140 ->151
0.14088
141 ->154
0.48503
142 ->153
-0.47731
Excited state symmetry could not be determined.
Excited State 65: Singlet-?Sym 4.7939 eV 258.63 nm f=0.0987
140 ->149
0.19418
140 ->150
0.16178
140 ->153
-0.13935
140 ->154
0.35824
141 ->149
-0.12571
141 ->151
0.23387
142 ->150
0.12369
143 ->153
0.11295
144 ->155
-0.10834
145 ->153
0.16023
148 ->157
-0.15230
Excited state symmetry could not be determined.
Excited State 66: Singlet-?Sym 4.7943 eV 258.61 nm f=0.0944
140 ->149
0.15822
140 ->150
-0.18965
140 ->153
0.36907
140 ->154
0.14167
141 ->150
-0.12232
142 ->149
-0.11976
142 ->151
-0.23347
143 ->155
-0.10999
145 ->154
-0.17949
146 ->156
-0.11445
148 ->156
-0.10743
Excited state symmetry could not be determined.
Excited State 67: Singlet-?Sym 4.8341 eV 256.48 nm f=0.1248
140 ->150
0.14734
140 ->153
0.42768
140 ->154
-0.29088
141 ->153
0.14199
141 ->154
0.10943
142 ->153
0.10866
142 ->154
-0.14334
331
APPENDIX D (continued)
145 ->154
0.12543
Excited state symmetry could not be determined.
Excited State 68: Singlet-?Sym 4.8342 eV 256.47 nm f=0.1262
140 ->149
-0.14673
140 ->153
0.28255
140 ->154
0.43122
141 ->153
0.11049
141 ->154
-0.14219
142 ->153
-0.14185
142 ->154
-0.11054
145 ->153
-0.11649
Excited state symmetry could not be determined.
Excited State 69: Singlet-?Sym 4.9337 eV 251.30 nm f=0.8485
140 ->151
0.36079
141 ->149
0.18822
142 ->150
0.18826
143 ->153
-0.15521
144 ->154
-0.15605
145 ->152
0.19223
Excited state symmetry could not be determined.
Excited State 70: Singlet-?Sym 5.0194 eV 247.01 nm f=0.0135
147 ->158
0.67696
148 ->158
0.10574
Excited state symmetry could not be determined.
Excited State 71: Singlet-?Sym 5.0203 eV 246.97 nm f=0.0132
146 ->158
0.67347
148 ->158
-0.12663
Excited state symmetry could not be determined.
Excited State 73: Singlet-?Sym 5.1352 eV 241.44 nm f=0.0145
146 ->159
-0.32223
146 ->160
-0.16167
147 ->159
-0.25444
147 ->160
0.42988
148 ->159
0.11946
148 ->160
0.29312
Excited state symmetry could not be determined.
Excited State 74: Singlet-?Sym 5.1371 eV 241.35 nm f=0.0055
332
APPENDIX D (continued)
147 ->159
148 ->159
148 ->160
0.25018
-0.45104
0.45817
Excited state symmetry could not be determined.
Excited State 75: Singlet-?Sym 5.1382 eV 241.30 nm f=0.0070
146 ->159
0.35629
146 ->160
0.24604
148 ->159
0.38231
148 ->160
0.38069
No.
1
2
4
5
6
7
8
9
11
12
13
14
15
16
17
18
19
20
22
23
25
26
27
28
29
30
31
32
34
Energy
(eV)
2.3379
2.3389
2.7349
2.7365
2.7872
2.8342
2.8355
2.9495
3.0136
3.0143
3.1398
3.1412
3.2863
3.2871
3.2930
3.3315
3.3322
3.3553
3.5100
3.5107
3.9406
3.9408
3.9431
4.0616
4.0926
4.0936
4.1132
4.1142
4.1707
Wavelength(nm)
530.33
530.09
453.34
453.08
444.83
437.46
437.26
420.35
411.42
411.32
394.88
394.70
377.28
377.18
376.51
372.15
372.08
369.52
353.23
353.16
314.63
314.62
314.43
305.26
302.95
302.87
301.43
301.35
297.28
f
0.0002
0.0003
0.0015
0.0013
0.0002
0.0238
0.0240
0.0002
0.0403
0.0394
0.0328
0.0321
0.0236
0.0246
0.0001
0.0059
0.0070
0.0241
0.0024
0.0024
0.0146
0.0146
0.0001
0.0016
0.0003
0.0003
0.0017
0.0018
0.0014
333
Symmetry
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Type
d-d
d-d
MLCT
MLCT
MLCT
MLCT
MLCT
MLCT
MLCT
MLCT
MLCT
MLCT
MLCT
MLCT
MLCT
MLCT
MLCT
MLCT
d-d
d-d
LLCT
LLCT
LLCT
ILCT
LLCT
LLCT
LLCT
LLCT
LLCT
APPENDIX D (continued)
35
36
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
60
61
62
64
65
66
67
68
69
70
71
73
74
75
4.1709
4.1978
4.2727
4.2739
4.3052
4.3072
4.3084
4.3835
4.3845
4.3885
4.4589
4.4596
4.4695
4.4794
4.4797
4.5045
4.5164
4.5172
4.5359
4.5371
4.5374
4.6061
4.6065
4.7036
4.7240
4.7241
4.7559
4.7939
4.7943
4.8341
4.8342
4.9337
5.0194
5.0203
5.1352
5.1371
5.1382
297.26
295.35
290.18
290.10
287.99
287.85
287.78
282.84
282.78
282.52
278.06
278.02
277.40
276.79
276.77
275.24
274.52
274.47
273.34
273.26
273.25
269.17
269.15
263.59
262.46
262.45
260.70
258.63
258.61
256.48
256.47
251.30
247.01
246.97
241.44
241.35
241.30
0.0014
0.0155
0.0079
0.0080
0.0016
0.0086
0.0083
0.0091
0.0089
0.0003
0.0039
0.0044
0.0001
0.0232
0.0221
0.0046
0.0085
0.0082
0.0163
0.0031
0.0031
0.0441
0.0452
0.0001
0.0688
0.0690
0.0027
0.0987
0.0944
0.1248
0.1262
0.8485
0.0135
0.0132
0.0145
0.0055
0.0070
334
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
LLCT
ILCT
MLCT
MLCT
LLCT
ILCT
LLCT
LLCT
ILCT
LLCT
MLCT
MLCT
ILCT
MLCT
MLLCT
MLCT
MLLCT
MLLCT
ILCT
LLCT
LLCT
LLCT
LLCT
ILCT
ILCT
ILCT
ILCT
ILCT
ILCT
ILCT
ILCT
ILCT
MLCT
MLCT
MLCT
MLCT
MLCT
APPENDIX D (continued)
Complex 4
This state for optimization and/or second-order correction.
Total Energy, E(RPA) = -1608.27906165
Copying the excited state density for this state as the 1-particle RhoCI density.
Excited state symmetry could not be determined.
Excited State 2: Singlet-?Sym 2.5014 eV 495.66 nm f=0.0070
127 ->140
-0.25982
129 ->130
0.40655
129 ->131
0.48330
Excited state symmetry could not be determined.
Excited State 3: Singlet-?Sym 2.5020 eV 495.54 nm f=0.0070
128 ->140
-0.26035
129 ->130
0.48366
129 ->131
-0.40634
Excited state symmetry could not be determined.
Excited State 6: Singlet-?Sym 2.6563 eV 466.76 nm f=0.0003
127 ->140
0.36139
127 ->141
-0.22885
127 ->144
0.18115
128 ->140
-0.10558
128 ->141
0.34465
128 ->144
-0.27320
129 ->130
0.18702
129 ->131
0.20672
Excited state symmetry could not be determined.
Excited State 7: Singlet-?Sym 2.6577 eV 466.51 nm f=0.0003
127 ->140
0.10880
127 ->141
0.34274
127 ->144
-0.27187
128 ->140
0.36438
128 ->141
0.22627
128 ->144
-0.17974
129 ->130
0.20620
129 ->131
-0.18762
Excited state symmetry could not be determined.
Excited State 8: Singlet-?Sym 2.7937 eV 443.80 nm f=0.0543
127 ->130
0.46661
335
APPENDIX D (continued)
127 ->131
128 ->130
128 ->131
129 ->132
0.11905
-0.11726
0.46723
-0.15587
Excited state symmetry could not be determined.
Excited State 10: Singlet-?Sym 2.9512 eV 420.12 nm f=0.0110
127 ->140
0.12320
128 ->133
0.66059
128 ->135
-0.11987
128 ->141
-0.11632
Excited state symmetry could not be determined.
Excited State 11: Singlet-?Sym 2.9526 eV 419.92 nm f=0.0109
127 ->133
0.66073
127 ->135
-0.11957
127 ->141
0.11817
128 ->140
-0.12020
Excited state symmetry could not be determined.
Excited State 12: Singlet-?Sym 3.0348 eV 408.54 nm f=0.0511
129 ->132
0.68040
Excited state symmetry could not be determined.
Excited State 13: Singlet-?Sym 3.1045 eV 399.37 nm f=0.0104
128 ->132
0.69803
Excited state symmetry could not be determined.
Excited State 14: Singlet-?Sym 3.1052 eV 399.28 nm f=0.0104
127 ->132
0.69810
Excited state symmetry could not be determined.
Excited State 19: Singlet-?Sym 3.9247 eV 315.91 nm f=0.0524
125 ->131
0.24728
126 ->130
0.19262
126 ->131
0.41826
129 ->135
-0.15331
129 ->136
-0.23113
129 ->137
-0.34622
Excited state symmetry could not be determined.
Excited State 20: Singlet-?Sym 3.9249 eV 315.89 nm f=0.0526
125 ->130
-0.24844
336
APPENDIX D (continued)
126 ->130
126 ->131
129 ->136
129 ->137
0.41870
-0.19140
0.36728
-0.24793
Excited state symmetry could not be determined.
Excited State 21: Singlet-?Sym 3.9757 eV 311.86 nm f=0.0177
129 ->134
0.69237
Excited state symmetry could not be determined.
Excited State 22: Singlet-?Sym 4.0167 eV 308.68 nm f=0.0028
125 ->130
0.43941
125 ->131
-0.15017
126 ->130
0.42002
126 ->131
-0.20263
129 ->136
-0.18217
129 ->137
0.11999
Excited state symmetry could not be determined.
Excited State 23: Singlet-?Sym 4.0169 eV 308.65 nm f=0.0029
125 ->130
0.15041
125 ->131
0.44005
126 ->130
-0.20144
126 ->131
-0.41952
129 ->136
-0.10971
129 ->137
-0.17303
Excited state symmetry could not be determined.
Excited State 24: Singlet-?Sym 4.0468 eV 306.38 nm f=0.0003
125 ->131
0.13059
127 ->135
-0.13956
128 ->134
0.66668
Excited state symmetry could not be determined.
Excited State 25: Singlet-?Sym 4.0473 eV 306.34 nm f=0.0003
125 ->130
0.12965
127 ->134
0.66452
128 ->135
-0.14781
Excited state symmetry could not be determined.
Excited State 26: Singlet-?Sym 4.0842 eV 303.57 nm f=0.0001
127 ->134
0.15564
127 ->135
0.14672
337
APPENDIX D (continued)
127 ->140
128 ->135
128 ->136
128 ->137
0.10577
0.59090
-0.12438
-0.16197
Excited state symmetry could not be determined.
Excited State 27: Singlet-?Sym 4.0847 eV 303.53 nm f=0.0001
127 ->135
0.59295
127 ->136
-0.12358
127 ->137
-0.16167
128 ->134
0.14769
128 ->135
-0.14741
128 ->140
-0.10558
Excited state symmetry could not be determined.
Excited State 29: Singlet-?Sym 4.1056 eV 301.99 nm f=0.0001
127 ->136
0.14229
127 ->137
-0.41067
128 ->136
0.52615
128 ->137
-0.14073
Excited state symmetry could not be determined.
Excited State 30: Singlet-?Sym 4.1208 eV 300.87 nm f=0.0001
127 ->136
-0.13743
127 ->137
0.45042
128 ->135
0.12789
128 ->136
0.42067
128 ->137
0.13704
129 ->135
-0.16356
Excited state symmetry could not be determined.
Excited State 31: Singlet-?Sym 4.1280 eV 300.35 nm f=0.0033
126 ->133
0.10894
127 ->136
0.48664
128 ->135
0.12287
128 ->137
0.46338
Excited state symmetry could not be determined.
Excited State 32: Singlet-?Sym 4.1511 eV 298.68 nm f=0.2935
125 ->130
0.38962
125 ->131
-0.10149
126 ->130
-0.15656
129 ->136
0.42487
338
APPENDIX D (continued)
129 ->137
-0.23548
Excited state symmetry could not be determined.
Excited State 33: Singlet-?Sym 4.1512 eV 298.67 nm f=0.2939
125 ->130
0.10098
125 ->131
0.38954
126 ->131
0.15798
129 ->135
0.17058
129 ->136
0.21306
129 ->137
0.40234
Excited state symmetry could not be determined.
Excited State 35: Singlet-?Sym 4.2485 eV 291.83 nm f=0.0093
125 ->132
0.49390
126 ->133
0.50042
Excited state symmetry could not be determined.
Excited State 37: Singlet-?Sym 4.4865 eV 276.35 nm f=0.0002
125 ->133
0.46173
126 ->132
-0.40761
129 ->135
0.12585
Excited state symmetry could not be determined.
Excited State 38: Singlet-?Sym 4.4888 eV 276.21 nm f=0.2019
123 ->130
-0.11563
124 ->131
0.11933
125 ->132
0.44417
126 ->133
-0.41727
127 ->139
-0.10307
128 ->138
0.10249
Excited state symmetry could not be determined.
Excited State 40: Singlet-?Sym 4.7511 eV 260.96 nm f=0.0001
123 ->131
0.50559
124 ->130
0.48262
Excited state symmetry could not be determined.
Excited State 41: Singlet-?Sym 4.7522 eV 260.90 nm f=0.0074
129 ->138
0.68036
Excited state symmetry could not be determined.
Excited State 42: Singlet-?Sym 4.7526 eV 260.88 nm f=0.0075
129 ->139
0.68262
339
APPENDIX D (continued)
Excited state symmetry could not be determined.
Excited State 43: Singlet-?Sym 4.8413 eV 256.10 nm f=0.0009
123 ->130
-0.32958
124 ->131
0.33145
127 ->138
0.18171
127 ->139
0.27997
128 ->138
-0.31528
128 ->139
0.19077
Excited state symmetry could not be determined.
Excited State 47: Singlet-?Sym 4.9609 eV 249.93 nm f=0.1134
123 ->132
0.17709
123 ->133
0.50690
124 ->133
0.37031
Excited state symmetry could not be determined.
Excited State 48: Singlet-?Sym 4.9610 eV 249.92 nm f=0.1111
123 ->133
-0.37129
124 ->132
-0.16470
124 ->133
0.51242
Excited state symmetry could not be determined.
Excited State 49: Singlet-?Sym 4.9819 eV 248.87 nm f=0.0609
123 ->132
-0.17874
123 ->133
-0.14220
124 ->132
0.62880
124 ->133
0.16798
Excited state symmetry could not be determined.
Excited State 50: Singlet-?Sym 4.9822 eV 248.85 nm f=0.0597
123 ->132
0.62934
123 ->133
-0.18572
124 ->132
0.17388
124 ->133
-0.14614
No.
2
3
6
7
8
Energy
(eV)
2.5014
2.5020
2.6563
2.6577
2.7937
Wavelength(nm)
495.66
495.54
466.76
466.51
443.80
f
0.0070
0.0070
0.0003
0.0003
0.0543
340
Symmetry
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Type
MLCT
MLCT
MLCT
MLCT
MLCT
APPENDIX D (continued)
10
11
12
13
14
19
20
21
22
23
24
25
26
27
29
30
31
32
33
35
37
38
40
41
42
43
47
48
49
50
2.9512
2.9526
3.0348
3.1045
3.1052
3.9247
3.9249
3.9757
4.0167
4.0169
4.0468
4.0473
4.0842
4.0847
4.1056
4.1208
4.1280
4.1511
4.1512
4.2485
4.4865
4.4888
4.7511
4.7522
4.7526
4.8413
4.9609
4.9610
4.9819
4.9822
420.12
419.92
408.54
399.37
399.28
315.91
315.89
311.86
308.68
308.65
306.38
306.34
303.57
303.53
301.99
300.87
300.35
298.68
298.67
291.83
276.35
276.21
260.96
260.90
260.88
256.10
249.93
249.92
248.87
248.85
0.0110
0.0109
0.0511
0.0104
0.0104
0.0524
0.0526
0.0177
0.0028
0.0029
0.0003
0.0003
0.0001
0.0001
0.0001
0.0001
0.0033
0.2935
0.2939
0.0093
0.0002
0.2019
0.0001
0.0074
0.0075
0.0009
0.1134
0.1111
0.0609
0.0597
341
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
Singlet-?Sym
MLCT
MLCT
MLCT
MLCT
MLCT
MLLCT
MLCT
LLCT
LLCT
LLCT
MLCT
MLCT
MLCT
MLCT
MLCT
MLCT
MLCT
MLLCT
MLLCT
ILCT
ILCT
ILCT
ILCT
MLCT
MLCT
MLLCT
LLCT
LLCT
ILCT
ILCT
APPENDIX E
CHAPTER 6 SUPPLEMENTARY INFORMATION
fac-Bipyrazyltricarbonyl(aquo)Rhenium(I) Hexafluorophosphate Dihydrate
Atomic coordinates (x 104) and equivalent isotropic displacement parameters(Ǻ2 x 103)
U(eq) is defined as one third of the trace of the orthogonalized Uij tensor.
_________________________________________________________
x
y
z
U(eq)
_________________________________________________________
C(1)
1842(10)
2500
7898(5)
29(2)
C(2)
349(6)
3529(4)
6711(3)
21(1)
C(3)
3717(7)
468(4)
6521(3)
25(1)
C(4)
4920(7)
-101(4)
6260(3)
26(1)
C(5)
6197(7)
1351(4)
5953(3)
26(1)
C(6)
5003(6)
1941(4)
6216(3)
21(1)
N(1)
3740(5)
1490(3)
6498(3)
20(1)
N(2)
6160(6)
325(4)
5969(3)
30(1)
O(1)
1725(7)
2500
8648(4)
39(2)
O(2)
-538(5)
4157(3)
6733(2)
33(1)
O(3)
2082(6)
2500
5302(3)
23(1)
O(4)
1305(6)
4311(4)
4780(3)
35(1)
F(1)
8379(7)
2500
8985(5)
70(2)
F(2)
5058(7)
2500
8363(4)
97(3)
F(3)
6150(14)
2500
9618(10)
114(11)
F(4)
6728(11)
1363(8)
8694(14)
199(11)
F(5)
7229(12)
2500
7707(10)
210(20)
F(6)
7109(12)
1709(15)
7978(11)
130(13)
F(7)
6419(14)
1680(19)
9302(11)
159(14)
P(1)
6719(2)
2500
8647(2)
28(1)
Re(1)
1865(1)
2500
6681(1)
17(1)
___________________________________________________________
342
APPENDIX E (continued)
Anisotropic displacement parameters (Ǻ2 x 103)
The anisotropic displacement factor exponent takes the form:
-2 π2 [ h2 a*2 U11 + ... + 2 h k a* b* U12 ]
__________________________________________________________________
U11
U22
U33
U23
U13
__________________________________________________________________
C(1)
40(5)
28(4)
19(4)
0
-8(4)
C(2)
21(3)
25(3)
17(2)
1(2)
1(2)
C(3)
32(3)
21(3)
23(3)
2(2)
-4(2)
C(4)
33(3)
18(3)
29(3)
3(2)
-8(2)
C(5)
28(3)
25(3)
27(3)
2(2)
-3(2)
C(6)
20(2)
21(3)
22(3)
2(2)
-2(2)
N(1)
25(2)
18(2)
17(2)
2(2)
-5(2)
N(2)
33(3)
23(3)
35(3)
-4(2)
-5(2)
O(1)
59(4)
45(4)
12(3)
0
1(3)
O(2)
32(2)
36(2)
31(2)
0(2)
1(2)
O(3)
34(3)
23(3)
13(2)
0
1(2)
O(4)
35(3)
25(2)
44(3)
7(2)
6(2)
F(1)
32(4)
98(6)
80(5)
0
-9(3)
F(2)
34(3)
188(10)
68(5)
0
-20(3)
F(3)
54(9)
240(30)
49(9)
0
30(8)
F(4)
97(9)
22(5)
480(30)
-36(13)
86(17)
F(5)
37(9)
560(70)
33(8)
0
4(6)
F(6)
190(30)
122(18)
77(12)
-80(14)
-89(14)
F(7)
126(17)
270(30)
81(12)
146(17)
-94(12)
P(1)
25(1)
25(1)
34(1)
0
3(1)
Re(1)
21(1)
17(1)
13(1)
0
-2(1)
U12
0
-1(2)
0(2)
1(2)
0(3)
3(2)
-1(2)
4(2)
0
11(2)
0
-3(2)
0
0
0
23(5)
0
115(18)
-163(19)
0
0
_____________________________________________________________________________
_
343
APPENDIX E (continued)
Bond lengths [Ǻ]
______________________________________________________________________
C(1)-O(1)
1.168(10)
F(1)-P(1)
1.583(6)
C(1)-Re(1)
1.888(8)
F(2)-P(1)
1.558(7)
C(2)-O(2)
1.145(6)
F(3)-F(7)#1
1.20(3)
C(2)-Re(1)
1.916(5)
F(3)-F(7)
1.20(3)
C(3)-N(1)
1.335(7)
F(3)-P(1)
1.592(15)
C(3)-C(4)
1.374(8)
F(4)-F(7)
1.07(3)
C(3)-H(3)
0.9300
F(4)-F(6)
1.25(3)
C(4)-N(2)
1.326(8)
F(4)-P(1)
1.488(11)
C(4)-H(4)
0.9300
F(5)-F(6)#1
1.12(2)
C(5)-N(2)
1.341(7)
F(5)-F(6)
1.12(2)
C(5)-C(6)
1.384(8)
F(5)-P(1)
1.528(16)
C(5)-H(5)
0.9300
F(6)-P(1)
1.505(15)
C(6)-N(1)
1.353(7)
F(7)-P(1)
1.502(14)
C(6)-C(6)#1
1.460(10)
P(1)-F(4)#1
1.488(11)
N(1)-Re(1)
2.161(5)
P(1)-F(7)#1
1.502(14)
O(3)-Re(1)
2.148(5)
P(1)-F(6)#1
1.505(15)
O(3)-H(103)
0.8200
Re(1)-C(2)#1
1.916(5)
O(4)-H(104)
0.66(2)
Re(1)-N(1)#1
2.161(5)
O(4)-H(105)
0.65(2)
344
APPENDIX E (continued)
Bond angles [deg]
________________________________________________________________________________
O(1)-C(1)-Re(1)
175.5(8)
F(4)#1-P(1)-F(6)#1
49.3(11)
O(2)-C(2)-Re(1)
178.7(5)
F(4)-P(1)-F(6)#1
135.9(13)
N(1)-C(3)-C(4)
121.4(6)
F(7)#1-P(1)-F(6)#1
91.1(13)
N(1)-C(3)-H(3)
119.3
F(7)-P(1)-F(6)#1
176.5(11)
C(4)-C(3)-H(3)
119.3
F(4)#1-P(1)-F(6)
135.9(14)
N(2)-C(4)-C(3)
122.4(5)
F(4)-P(1)-F(6)
49.3(11)
N(2)-C(4)-H(4)
118.8
F(7)#1-P(1)-F(6)
176.5(11)
C(3)-C(4)-H(4)
118.8
F(7)-P(1)-F(6)
91.1(13)
N(2)-C(5)-C(6)
122.2(6)
F(6)#1-P(1)-F(6)
86.7(17)
N(2)-C(5)-H(5)
118.9
F(4)#1-P(1)-F(5)
92.6(9)
C(6)-C(5)-H(5)
118.9
F(4)-P(1)-F(5)
92.6(9)
N(1)-C(6)-C(5)
120.3(5)
F(7)#1-P(1)-F(5)
134.4(10)
N(1)-C(6)-C(6)#1
115.8(3)
F(7)-P(1)-F(5)
134.4(10)
C(5)-C(6)-C(6)#1
123.9(3)
F(6)#1-P(1)-F(5)
43.4(9)
C(3)-N(1)-C(6)
117.2(5)
F(6)-P(1)-F(5)
43.4(9)
C(3)-N(1)-Re(1)
126.5(4)
F(4)#1-P(1)-F(2)
91.1(4)
C(6)-N(1)-Re(1)
115.6(3)
F(4)-P(1)-F(2)
91.1(4)
C(4)-N(2)-C(5)
116.5(5)
F(7)#1-P(1)-F(2)
91.1(4)
Re(1)-O(3)-H(103)
109.5
F(7)-P(1)-F(2)
91.1(4)
H(104)-O(4)-H(105)
117(10)
F(6)#1-P(1)-F(2)
91.7(4)
F(7)#1-F(3)-F(7)
126(2)
F(6)-P(1)-F(2)
91.7(4)
F(7)#1-F(3)-P(1)
63.2(10)
F(5)-P(1)-F(2)
91.1(5)
F(7)-F(3)-P(1)
63.2(10)
F(4)#1-P(1)-F(1)
88.8(4)
F(7)-F(4)-F(6)
135.9(18)
F(4)-P(1)-F(1)
88.8(4)
F(7)-F(4)-P(1)
69.8(12)
F(7)#1-P(1)-F(1)
86.9(4)
F(6)-F(4)-P(1)
66.1(10)
F(7)-P(1)-F(1)
86.9(4)
F(6)#1-F(5)-F(6)
134(3)
F(6)#1-P(1)-F(1)
90.5(4)
F(6)#1-F(5)-P(1)
67.2(13)
F(6)-P(1)-F(1)
90.5(4)
F(6)-F(5)-P(1)
67.2(13)
F(5)-P(1)-F(1)
91.8(5)
F(5)-F(6)-F(4)
134.1(19)
F(2)-P(1)-F(1)
177.1(4)
F(5)-F(6)-P(1)
69.4(13)
F(4)#1-P(1)-F(3)
87.4(9)
F(4)-F(6)-P(1)
64.6(9)
F(4)-P(1)-F(3)
87.4(9)
F(4)-F(7)-F(3)
139(2)
F(7)#1-P(1)-F(3)
45.7(11)
F(4)-F(7)-P(1)
68.4(10)
F(7)-P(1)-F(3)
45.7(11)
F(3)-F(7)-P(1)
71.1(14)
F(6)#1-P(1)-F(3)
136.7(9)
F(4)#1-P(1)-F(4)
174.3(17)
F(6)-P(1)-F(3)
136.7(9)
F(4)#1-P(1)-F(7)#1
41.8(12)
F(5)-P(1)-F(3)
178.7(6)
F(4)-P(1)-F(7)#1
132.9(15)
F(2)-P(1)-F(3)
87.6(6)
F(4)#1-P(1)-F(7)
132.9(15)
F(1)-P(1)-F(3)
89.4(5)
F(4)-P(1)-F(7)
41.8(12)
C(1)-Re(1)-C(2)#1
88.2(2)
F(7)#1-P(1)-F(7)
91(2)
C(1)-Re(1)-C(2)
88.2(2)
345
APPENDIX E (continued)
C(2)#1-Re(1)-C(2)
C(1)-Re(1)-O(3)
C(2)#1-Re(1)-O(3)
C(2)-Re(1)-O(3)
C(1)-Re(1)-N(1)#1
C(2)#1-Re(1)-N(1)#1
C(2)-Re(1)-N(1)#1
89.1(3)
175.4(3)
95.08(18)
95.08(18)
98.1(2)
171.02(18)
97.5(2)
O(3)-Re(1)-N(1)#1
C(1)-Re(1)-N(1)
C(2)#1-Re(1)-N(1)
C(2)-Re(1)-N(1)
O(3)-Re(1)-N(1)
N(1)#1-Re(1)-N(1)
78.33(16)
98.1(2)
97.5(2)
171.02(18)
78.33(16)
75.3(2)
4b,5,7,7a-Tetrahydro-4b,7a-Epiminomethanoimino-6H-Imidazo [4,5-f][1,10]Phenanthroline6,13-dione Monohydrate
Atomic coordinates (x 104) and equivalent isotropic displacement parameters(Ǻ2 x 103)
U(eq) is defined as one third of the trace of the orthogonalized Uij tensor.
__________________________________________________________
x
y
z
U(eq)
__________________________________________________________
C(1)
5754(1)
5105(1)
2304(1)
25(1)
C(2)
5211(1)
4480(1)
1555(1)
27(1)
C(3)
4475(1)
4494(1)
1603(1)
24(1)
C(4)
4311(1)
5115(1)
2410(1)
17(1)
C(5)
4899(1)
5701(1)
3149(1)
16(1)
C(6)
4769(1)
6349(1)
4059(1)
17(1)
C(7)
4060(1)
6364(1)
4221(1)
16(1)
C(8)
3979(1)
6947(1)
5116(1)
23(1)
C(9)
4603(1)
7481(1)
5806(1)
26(1)
C(10)
5284(1)
7433(1)
5572(1)
24(1)
C(11)
3499(1)
5180(1)
2437(1)
15(1)
C(12)
3391(1)
5727(1)
3491(1)
16(1)
C(13)
3069(1)
3917(1)
3465(1)
18(1)
C(14)
2520(1)
6436(1)
1881(1)
18(1)
C(15)
-1058(1)
-179(2)
1688(1)
30(1)
C(16)
-649(1)
-1125(1)
1984(1)
29(1)
C(17)
113(1)
-1120(1)
2081(1)
24(1)
C(18)
432(1)
-185(1)
1813(1)
18(1)
C(19)
-37(1)
706(1)
1432(1)
19(1)
C(20)
242(1)
1673(1)
989(1)
19(1)
C(21)
1020(1)
1812(1)
1161(1)
18(1)
C(22)
1251(1)
2708(1)
691(1)
23(1)
C(23)
708(1)
3428(1)
80(1)
28(1)
C(24)
-52(1)
3220(1)
-51(1)
27(1)
C(25)
1282(1)
-125(1)
2000(1)
17(1)
346
APPENDIX E (continued)
C(26)
C(27)
C(28)
N(1)
N(2)
N(3)
N(4)
N(5)
N(6)
N(7)
N(8)
N(9)
N(10)
N(11)
N(12)
O(1)
O(2)
O(3)
O(4)
O(1S)
O(2S)
1590(1)
1031(1)
1893(1)
17(1)
2149(1)
-246(1)
1047(1)
20(1)
2035(1)
514(1)
3734(1)
21(1)
5611(1)
5709(1)
3084(1)
21(1)
5374(1)
6891(1)
4717(1)
22(1)
3182(1)
4111(1)
2483(1)
19(1)
3238(1)
4816(1)
4097(1)
20(1)
3031(1)
5845(1)
1534(1)
19(1)
2732(1)
6407(1)
3001(1)
20(1)
-769(1)
725(1)
1414(1)
25(1)
-287(1)
2363(1)
385(1)
26(1)
1535(1)
-739(1)
1221(1)
20(1)
2203(1)
773(1)
1455(1)
20(1)
1707(1)
-368(1)
3155(1)
21(1)
1848(1)
1393(1)
3038(1)
20(1)
2850(1)
3054(1)
3748(1)
26(1)
1967(1)
6922(1)
1263(1)
24(1)
2579(1)
-652(1)
597(1)
27(1)
2421(1)
557(1)
4720(1)
30(1)
1795(1)
7536(1)
4047(1)
21(1)
3234(1)
2710(1)
6065(1)
20(1)
__________________________________________________________
347
APPENDIX E (continued)
Anisotropic displacement parameters (Ǻ2 x 103)
The anisotropic displacement factor exponent takes the form:
-2 π2 [ h2 a*2 U11 + ... + 2 h k a* b* U12 ]
__________________________________________________________________
U11
U22
U33
U23
U13
__________________________________________________________________
C(1)
19(1)
32(1)
27(1)
-4(1)
11(1)
C(2)
28(1)
29(1)
28(1)
-9(1)
15(1)
C(3)
24(1)
24(1)
24(1)
-7(1)
10(1)
C(4)
19(1)
15(1)
17(1)
2(1)
7(1)
C(5)
17(1)
16(1)
16(1)
3(1)
5(1)
C(6)
18(1)
15(1)
16(1)
2(1)
3(1)
C(7)
18(1)
15(1)
15(1)
1(1)
4(1)
C(8)
23(1)
25(1)
24(1)
-5(1)
11(1)
C(9)
29(1)
28(1)
22(1)
-10(1)
8(1)
C(10)
22(1)
24(1)
24(1)
-8(1)
2(1)
C(11)
17(1)
15(1)
14(1)
-2(1)
4(1)
C(12)
15(1)
17(1)
16(1)
0(1)
6(1)
C(13)
13(1)
21(1)
18(1)
2(1)
2(1)
C(14)
18(1)
16(1)
20(1)
0(1)
5(1)
C(15)
18(1)
38(1)
35(1)
11(1)
10(1)
C(16)
24(1)
29(1)
35(1)
10(1)
9(1)
C(17)
23(1)
22(1)
26(1)
6(1)
7(1)
C(18)
18(1)
21(1)
16(1)
0(1)
5(1)
C(19)
17(1)
23(1)
17(1)
1(1)
5(1)
C(20)
19(1)
20(1)
19(1)
0(1)
5(1)
C(21)
19(1)
17(1)
17(1)
-1(1)
6(1)
C(22)
20(1)
22(1)
27(1)
2(1)
8(1)
C(23)
28(1)
23(1)
33(1)
9(1)
12(1)
C(24)
24(1)
23(1)
33(1)
11(1)
6(1)
C(25)
18(1)
15(1)
17(1)
1(1)
4(1)
C(26)
15(1)
17(1)
19(1)
-1(1)
5(1)
C(27)
19(1)
21(1)
19(1)
1(1)
6(1)
C(28)
20(1)
21(1)
20(1)
0(1)
5(1)
N(1)
17(1)
24(1)
23(1)
-2(1)
6(1)
N(2)
19(1)
23(1)
22(1)
-4(1)
4(1)
N(3)
22(1)
16(1)
20(1)
-4(1)
8(1)
N(4)
24(1)
21(1)
16(1)
0(1)
10(1)
N(5)
20(1)
22(1)
13(1)
0(1)
4(1)
N(6)
18(1)
26(1)
17(1)
-2(1)
5(1)
N(7)
17(1)
30(1)
29(1)
7(1)
8(1)
N(8)
20(1)
24(1)
32(1)
7(1)
6(1)
N(9)
22(1)
17(1)
25(1)
-4(1)
11(1)
348
U12
1(1)
-2(1)
-6(1)
0(1)
1(1)
1(1)
0(1)
-3(1)
-2(1)
-3(1)
-2(1)
0(1)
-1(1)
-1(1)
-2(1)
-6(1)
0(1)
-2(1)
-1(1)
1(1)
0(1)
-1(1)
2(1)
5(1)
0(1)
-1(1)
1(1)
1(1)
0(1)
-1(1)
-4(1)
-5(1)
2(1)
7(1)
1(1)
3(1)
-3(1)
APPENDIX E (continued)
N(10)
16(1)
18(1)
29(1)
0(1)
10(1)
-2(1)
N(11)
22(1)
17(1)
19(1)
4(1)
2(1)
-1(1)
N(12)
23(1)
16(1)
18(1)
-1(1)
2(1)
-3(1)
O(1)
28(1)
23(1)
23(1)
2(1)
6(1)
-10(1)
O(2)
23(1)
24(1)
22(1)
4(1)
2(1)
6(1)
O(3)
28(1)
26(1)
32(1)
-3(1)
18(1)
0(1)
O(4)
35(1)
28(1)
18(1)
1(1)
-2(1)
-2(1)
O(1S)
22(1)
20(1)
22(1)
1(1)
9(1)
-1(1)
O(2S)
19(1)
21(1)
20(1)
1(1)
7(1)
-2(1)
________________________________________________________________________
Bond lengths [Ǻ]
_________________________________________________________________________
C(1)-N(1)
1.332(2)
C(14)-O(2)
1.2312(18)
C(1)-C(2)
1.380(2)
C(14)-N(6)
1.3490(19)
C(1)-H(1)
0.9300
C(14)-N(5)
1.3756(19)
C(2)-C(3)
1.382(2)
C(15)-N(7)
1.334(2)
C(2)-H(2)
0.9300
C(15)-C(16)
1.381(2)
C(3)-C(4)
1.390(2)
C(15)-H(15)
0.9300
C(3)-H(3A)
0.9300
C(16)-C(17)
1.377(2)
C(4)-C(5)
1.395(2)
C(16)-H(16)
0.9300
C(4)-C(11)
1.515(2)
C(17)-C(18)
1.391(2)
C(5)-N(1)
1.3474(19)
C(17)-H(17)
0.9300
C(5)-C(6)
1.487(2)
C(18)-C(19)
1.393(2)
C(6)-N(2)
1.3462(19)
C(18)-C(25)
1.516(2)
C(6)-C(7)
1.391(2)
C(19)-N(7)
1.3471(19)
C(7)-C(8)
1.394(2)
C(19)-C(20)
1.485(2)
C(7)-C(12)
1.5120(19)
C(20)-N(8)
1.3428(19)
C(8)-C(9)
1.377(2)
C(20)-C(21)
1.396(2)
C(8)-H(8)
0.9300
C(21)-C(22)
1.391(2)
C(9)-C(10)
1.386(2)
C(21)-C(26)
1.513(2)
C(9)-H(9A)
0.9300
C(22)-C(23)
1.383(2)
C(10)-N(2)
1.330(2)
C(22)-H(22)
0.9300
C(10)-H(10A)
0.9300
C(23)-C(24)
1.387(2)
C(11)-N(5)
1.4548(18)
C(23)-H(23)
0.9300
C(11)-N(3)
1.4569(19)
C(24)-N(8)
1.334(2)
C(11)-C(12)
1.5691(19)
C(24)-H(24)
0.9300
C(12)-N(4)
1.4435(19)
C(25)-N(9)
1.4397(19)
C(12)-N(6)
1.4502(18)
C(25)-N(11)
1.4591(18)
C(13)-O(1)
1.2362(18)
C(25)-C(26)
1.563(2)
C(13)-N(4)
1.350(2)
C(26)-N(12)
1.4498(19)
C(13)-N(3)
1.3506(19)
C(26)-N(10)
1.4500(19)
349
APPENDIX E (continued)
C(27)-O(3)
C(27)-N(10)
C(27)-N(9)
C(28)-O(4)
C(28)-N(11)
C(28)-N(12)
N(3)-H(3)
N(4)-H(4)
N(5)-H(5)
1.2253(18)
1.356(2)
1.370(2)
1.2302(18)
1.349(2)
1.376(2)
0.826(19)
0.85(2)
0.84(2)
N(6)-H(6)
N(9)-H(9)
N(10)-H(10)
N(11)-H(11)
N(12)-H(12)
O(1S)-H(1S)
O(1S)-H(2S)
O(2S)-H(3S)
O(2S)-H(4S)
0.8600
0.86(2)
0.8600
0.8600
0.90(2)
0.84(2)
0.87(2)
0.83(3)
0.87(2)
Bond angles [deg]
________________________________________________________________________________
N(1)-C(1)-C(2)
123.60(14)
N(5)-C(11)-N(3)
113.56(11)
N(1)-C(1)-H(1)
118.2
N(5)-C(11)-C(4)
111.02(11)
C(2)-C(1)-H(1)
118.2
N(3)-C(11)-C(4)
111.58(12)
C(1)-C(2)-C(3)
118.36(14)
N(5)-C(11)-C(12)
102.77(11)
C(1)-C(2)-H(2)
120.8
N(3)-C(11)-C(12)
101.37(11)
C(3)-C(2)-H(2)
120.8
C(4)-C(11)-C(12)
116.03(11)
C(2)-C(3)-C(4)
119.27(14)
N(4)-C(12)-N(6)
113.68(12)
C(2)-C(3)-H(3A)
120.4
N(4)-C(12)-C(7)
110.09(11)
C(4)-C(3)-H(3A)
120.4
N(6)-C(12)-C(7)
111.97(12)
C(3)-C(4)-C(5)
118.46(13)
N(4)-C(12)-C(11)
102.45(11)
C(3)-C(4)-C(11)
119.83(13)
N(6)-C(12)-C(11)
101.72(11)
C(5)-C(4)-C(11)
121.66(13)
C(7)-C(12)-C(11)
116.50(11)
N(1)-C(5)-C(4)
122.18(13)
O(1)-C(13)-N(4)
125.22(14)
N(1)-C(5)-C(6)
116.57(12)
O(1)-C(13)-N(3)
125.71(14)
C(4)-C(5)-C(6)
121.25(13)
N(4)-C(13)-N(3)
109.07(13)
N(2)-C(6)-C(7)
122.63(13)
O(2)-C(14)-N(6)
126.14(14)
N(2)-C(6)-C(5)
116.33(13)
O(2)-C(14)-N(5)
124.99(14)
C(7)-C(6)-C(5)
121.03(13)
N(6)-C(14)-N(5)
108.86(12)
C(6)-C(7)-C(8)
118.60(13)
N(7)-C(15)-C(16)
123.63(15)
C(6)-C(7)-C(12)
121.99(13)
N(7)-C(15)-H(15)
118.2
C(8)-C(7)-C(12)
119.35(13)
C(16)-C(15)-H(15)
118.2
C(9)-C(8)-C(7)
118.79(14)
C(17)-C(16)-C(15)
118.47(15)
C(9)-C(8)-H(8)
120.6
C(17)-C(16)-H(16)
120.8
C(7)-C(8)-H(8)
120.6
C(15)-C(16)-H(16)
120.8
C(8)-C(9)-C(10)
118.66(14)
C(16)-C(17)-C(18)
119.06(15)
C(8)-C(9)-H(9A)
120.7
C(16)-C(17)-H(17)
120.5
C(10)-C(9)-H(9A)
120.7
C(18)-C(17)-H(17)
120.5
N(2)-C(10)-C(9)
123.69(14)
C(17)-C(18)-C(19)
118.50(13)
N(2)-C(10)-H(10A)
118.2
C(17)-C(18)-C(25)
120.24(13)
C(9)-C(10)-H(10A)
118.2
C(19)-C(18)-C(25)
121.16(13)
350
APPENDIX E (continued)
N(7)-C(19)-C(18)
N(7)-C(19)-C(20)
C(18)-C(19)-C(20)
N(8)-C(20)-C(21)
N(8)-C(20)-C(19)
C(21)-C(20)-C(19)
C(22)-C(21)-C(20)
C(22)-C(21)-C(26)
C(20)-C(21)-C(26)
C(23)-C(22)-C(21)
C(23)-C(22)-H(22)
C(21)-C(22)-H(22)
C(22)-C(23)-C(24)
C(22)-C(23)-H(23)
C(24)-C(23)-H(23)
N(8)-C(24)-C(23)
N(8)-C(24)-H(24)
C(23)-C(24)-H(24)
N(9)-C(25)-N(11)
N(9)-C(25)-C(18)
N(11)-C(25)-C(18)
N(9)-C(25)-C(26)
N(11)-C(25)-C(26)
C(18)-C(25)-C(26)
N(12)-C(26)-N(10)
N(12)-C(26)-C(21)
N(10)-C(26)-C(21)
N(12)-C(26)-C(25)
N(10)-C(26)-C(25)
C(21)-C(26)-C(25)
O(3)-C(27)-N(10)
O(3)-C(27)-N(9)
N(10)-C(27)-N(9)
O(4)-C(28)-N(11)
O(4)-C(28)-N(12)
N(11)-C(28)-N(12)
C(1)-N(1)-C(5)
C(10)-N(2)-C(6)
C(13)-N(3)-C(11)
C(13)-N(3)-H(3)
C(11)-N(3)-H(3)
C(13)-N(4)-C(12)
C(13)-N(4)-H(4)
122.23(14)
116.68(13)
121.06(13)
122.67(14)
116.78(13)
120.48(13)
118.35(13)
121.59(13)
119.99(13)
119.15(14)
120.4
120.4
118.45(15)
120.8
120.8
123.45(15)
118.3
118.3
113.03(12)
114.54(12)
110.39(12)
102.53(11)
100.47(11)
114.90(12)
113.83(12)
111.15(12)
112.60(12)
102.11(11)
100.56(11)
115.86(11)
125.48(14)
125.99(14)
108.53(13)
127.22(14)
124.43(14)
108.33(12)
118.09(13)
117.59(13)
112.40(12)
121.0(12)
123.4(12)
112.16(12)
122.0(13)
C(12)-N(4)-H(4)
C(14)-N(5)-C(11)
C(14)-N(5)-H(5)
C(11)-N(5)-H(5)
C(14)-N(6)-C(12)
C(14)-N(6)-H(6)
C(12)-N(6)-H(6)
C(15)-N(7)-C(19)
C(24)-N(8)-C(20)
C(27)-N(9)-C(25)
C(27)-N(9)-H(9)
C(25)-N(9)-H(9)
C(27)-N(10)-C(26)
C(27)-N(10)-H(10)
C(26)-N(10)-H(10)
C(28)-N(11)-C(25)
C(28)-N(11)-H(11)
C(25)-N(11)-H(11)
C(28)-N(12)-C(26)
C(28)-N(12)-H(12)
C(26)-N(12)-H(12)
H(1S)-O(1S)-H(2S)
H(3S)-O(2S)-H(4S)
351
120.8(13)
110.37(12)
117.7(13)
115.4(13)
113.08(12)
123.5
123.5
117.70(14)
117.93(13)
110.09(12)
119.0(13)
122.6(13)
112.37(12)
123.8
123.8
112.65(12)
123.7
123.7
109.51(12)
116.7(12)
117.7(12)
104(2)
106(2)
352