2008

I hereby certify that this material, which I now submit for assessment on the programme of study leading to the award of Doctor of Philosophy by research and thesis, is entirely my own work and has not been taken from work of others, save and to the extent that such work has been cited within the text of my work.
Signed:
Lynda Cassidy
Student I.D. No.:
Date:
50064483 ii

Chapter 1 is an introductory chapter and is primarily concerned with presenting the main topic of this thesis, the use of diverse synthetic methods in the development and design of large multinuclear transition metal complexes. It begins with an introduction to the concept of supramolecular chemistry and some of the most important features of supramolecular systems. The basic concepts regarding Ru(II) polypyridyl chemistry are introduced and explained, as such complexes often serve as building blocks in supramolecules. This is followed by an extensive discussion on both the traditional and novel synthetic techniques available within inorganic synthesis.
The next chapters of this thesis describe the synthesis and characterization of mononuclear and dinuclear ruthenium (II) and osmium (II) complexes using various synthetic methods. The experimental methodology used to synthesize and characterize these complexes is detailed in chapter 2.
The investigation into synthetic techniques for the development of ruthenium (II) and osmium (II) multinuclear metal complexes begins with chapter 3. This chapter is concerned with the use of the synthetic strategy of
“complexes as metals / complexes as ligands”
in the formation of these complexes. This previously reported method is used to synthesis the homodinuclear complex [Ru(bpy)
2
(bpt)Ru(tpy)Cl]
2+ and the heterodinuclear complex [Os(bpy)
2
(bpt)Ru(tpy)Cl]
2+
. These complexes are fully characterized via NMR, mass spectrometry and CHN with a discussion of their electronic and electrochemical properties included.
Chapter 4 continues with the investigation into synthetic techniques and provides an alternative synthetic approach to the one discussed in chapter 3. Here the first coupling method, Suzuki cross-coupling, is introduced. This method is extensively used in the formation of asymmetrical compounds and is used here for the purpose of synthesizing an asymmetrically bridged ruthenium dinuclear complex. This chapter provides an iii

overview of this catalytic cycle and the attempted synthesis of the desired ruthenium dinuclear complex using this method is discussed.
Chapter 5 follows on from chapter 4 and presents the second cross-coupling reaction used in this thesis, in the form of the Ni(0) coupling reaction. This method is used in the formation of homodinuclear and heterodinuclear complexes bound with symmetrical or asymmetrical bridging ligands based on bipyridyl and pyridyl-triazole ligands. Once again full characterization of these complexes is provided, along with a detailed discussion of the synthetic method.
Chapter 6 sees the conclusion on the discussion of the complexes synthesized via Ni(0) coupling, with an extensive examination of all the electronic and electrochemical data retrieved.
Finally we conclude with a summary of the work completed in this thesis and possible future work in chapter 7. iv

Table of Contents
Authors Declaration
Abstract
Table of Contents
Chapter 3 Synthesis and Characterisation of Novel
[M(bpy)
2
(bpt)Ru(tpy)Cl] 2+ type complexes
3.1 Introduction
Chapter 1 Introduction
1.1 Supramolecular Chemistry
1.2 Metal (II) Polypyridyl Complexes
1.2.1 Examination of Ligand and Metal Orbitals
1.2.2 Properties of [Ru(bpy)
3
]
2+
and [Os(bpy)
3
]
2+
1.3 Synthetic Strategies
1.3.1
“Complexes as Metals/Complexes as Ligands”
Strategy
1.3.2 Cross-Coupling Reactions
1.4 Scope of Thesis
1.5 Bibliography
Chapter 2 Instrumental Methods
2.1 Instrumental Methods
2.1.1 Structural Characterization
2.1.2 Photophysical and Electrochemical Characterization
2.2 General Synthetic Methods
2.2.1 General Synthesis of Starting Materials
2.3 Bibliography
44
45
45
46
47
48
51
52
53
1
2
6
6
10
14 ii iii v
17
30
38
40 v

3.2 Experimental
3.2.1 Synthesis of Ligands
3.2.2 Synthesis of Mononuclear Complexes
3.2.3 Synthesis of Dinuclear Complexes
3.3 Results and Discussion
3.3.1 Synthesis of Mononuclear and Dinuclear Complexes
3.3.2 Mass Spectrometry of Novel Dinuclear Complexes
3.3.3 1 H-NMR Characterization
3.3.3.1
1
H-NMR of Mononuclear Complexes
3.3.3.2
1
H-NMR of Dinuclear Complexes
3.3.4 UV-Vis Absorption and Emission Spectroscopy of
Novel Metal Complexes and Model Compounds
3.3.5 Electrochemical Properties
3.4 Conclusions
3.5 Bibliography
Chapter 4 Synthesis of Dinuclear Triazole Containing
Complexes via Suzuki Cross-Coupling
4.1 Introduction
4.2 Experimental
4.2.1 Synthesis of Ligands
4.2.1.1 Attempted Ligand Syntheses
4.2.2 Synthesis of Mononuclear Complexes
4.2.3 Suzuki Cross-Coupling Reactions
4.3 Results and Discussion
4.3.1 Precursor Complexes
4.3.1.1 Attempted Precursor Complexes
4.3.2 Suzuki Coupling Reactions
4.4 Conclusions
4.5 Bibliography
93
100
108
110
72
72
76
82
63
63
64
67
82
85
112
113
130
132
132
137
124
124
126
128
140
146
148 vi

Chapter 5 Synthesis of Dinuclear Complexes via Ni(0)
Cross-Coupling
5.1 Introduction
5.1.2 Ni(0) Cross-Coupling
5.2 Experimental
5.2.1 Synthesis of Mononuclear Metal Complexes
5.2.1 Ni(0) Cross-Coupling Reactions
5.3 Results and Discussion
5.3.1 Synthetic Aspects
5.3.2 Mass Spectrometry of Dinuclear Complexes
5.3.3 NMR Characterization
5.3.3.1
1
H-NMR Characterization of Asymmetrically
Bridged Dinuclear Complexes
5.3.3.2
1
H-NMR Characterization of Symmetrically
5.4 Conclusions
Bridged Dinuclear Complexes
5.5 Bibliography
Chapter 6 Electronic & Electrochemical Properties of
Dinuclear Complexes Synthesized via Ni(0)
Coupling
6.1 Introduction
6.2 Electronic Properties of Dinuclear Complexes
6.2.1 Acid/Base Chemistry of Dinuclear Complexes
6.3 Electrochemical Properties of Dinuclear Complexes
6.4 Conclusions
6.5 Bibliography
1451
166
173
173
179
183
152
155
163
163
184
190
197
199
202
203
207
216
222
234
236 vii

Chapter 7 Conclusions and Future Work
7.1 Conclusions and Future Work
238
239
Appendix Spectroelectrochemical Analysis of Heterodinuclear
Complexes Synthesized via Ni(0) Coupling 242 viii