Supplementary Material:
Steady state spectroscopy of the 2-(N-methylacetimidoyl)-1-naphthol
molecule
Juan Carlos del Valle, Cristina Díaz-Oliva
Department of Applied Physical Chemistry, Universidad Autónoma de Madrid, E28049, Cantoblanco, Madrid. Juan.valle@uam.es
enol*
enol*
S1
E
em
abs
em
enol
So
cis-keto*
S 'o
So
enol
Model 2. Douhal, Lahmani,
Zehnacker-Rentien
Model 1. Catalán, del Valle
enol*
S '1
em
E
abs
cis-keto*
S1
enol*
trans-keto*
cis-keto*
trans-keto*
S1
S1
S '1
S '1
S ''1
S ''1
E
em
em
abs
S'
So
cis-keto
em
abs
S'
S 'o'
o
enol
E
non-radiative
S 'o'
o
So
trans-keto
enol
trans-keto
cis-keto
Model 3. Tobita, Yamamoto, Kurahayashi, Model 4. Organero, Moreno, Santos,
Lluch, Douhal
Tsukagoshi, Nakamura, Shizuka
O
H
O
O
CH3
Enol
OH normal tautomer
H
O
O
CH3
cis-Keto
proton transfer tautomer
CH3
OH
trans-Keto
proton transfer tautomer
enol*
cis-keto*
S1
enol*
S 1'
S1
cis-keto*
S '1
trans-keto*
S ''1
em
E
abs
em
E
S'
em
abs
o
o
So
enol
S'
S ''o
trans-keto
So
cis-keto
cis-keto
enol
Model 6 Ortiz-Sánchez, Gelabert, Moreno
Lluch
Model 5 Lochbrunner, Szeghalmi
Stock, Schmitt
enol*
enol-1*
S1
E
cis-keto*
S 1'
em
em
So
S 'o
S ''1
x
abs
enol
enol-1
S ''o
cis-keto
Model 7 Catalan, De Paz
Models reported in the literature on the photophemistry and photostability of the 1hydroxy-2-acetonaphthone molecule (HAN). The oblique line means that the state
energy does not correspond to an energy minimum.
Modelo 1. J. Catalán, J.C. del Valle. J. Am. Chem. Soc., 1993, 115, 4321.
Modelo 2. A. Douhal, F. Lahmani and A. Zehnacker-Rentien, Chem.
Phys. 178 (1993) 493.
Modelo 3. S. Tobita, M. Yamamoto, N. Kurahayashi, R. Tsukagoshi, Y. Nakamura, H.
Shizuka. J. Phys. Chem. A 1998, 102, 5206-5214.
Modelo 4. J. A. Organero, M. Moreno, L. Santos, J. M. Lluch, A. Douhal. J. Phys.
Chem. A 2000, 104, 8424-8431.
Modelo 5. S. Lochbrunner, A. Szeghalmi, K. Stock, M. Schmitt. J. Chem. Phys. 2005,
122, 244315(1-9).
Modelo 6. J. M. Ortiz-Sánchez, R. Gelabert, M. Moreno, J. M. Lluch. J. Chem. Phys.
2007, 127, 84318 (1-8).
Modelo 7. J. Catalán, J. L.G. de Paz. J. Phys. Chem. A 2008, 112, 904-914.
Energy (kcal/mol)
90
85
80
5
0
1,0
1,5
2,0
O-H (Angstroms)
Figure S1. Potential energy curves as a function of the donor O-H distance for the ground
electronic state and the first excited electronic state of the HAN molecule. In black dots, the
calculations at the TD-DFT/B3LYP//TZVP level (Catalán, J. and J. L.G. de Paz (2008) On the
Inoperativeness of the ESIPT Process in the Emission of 1-Hydroxy-2-acetonaphthone: A
Reappraisal J. Phys. Chem. A 112, 904-914), with full excited state geometry optimization, in
white dots, the calculations at the TD-B3LYP/6-31G** level for geometries along the reaction
path in the first excited state calculated at the CIS/6-31G** level (calculated herein), both of
them are presented for comparison. The comparison is reasonably good from a qualitative
point of view. Both curves in the ground electronic state or in the first excited electronic state
are normalized to the respective energy minimum.
E
kcal/mol
H
O
CH3
H
O
N
CH3
CH3
N
CH3
15.1
O
O
N
H
O
H
N
CH3
N
CH3
14.5
CH3
H
CH3
CH3
13.6
10.7
O
CH3
H
N
CH3
CH3
0.9
0.0
Figure S2. Ground electronic-state energies for some of the isomers studied referred to the
NH-tautomers as origin. The calculations have been executed at the DFT-B3LYP level with 631G** basis set and full geometry optimization. The vibrational analyses were done and all of
the structures shown possess all the vibrational frequencies as positive. The OH-tautomer
molecule with state energies 0.9 and the NH-tautomers are considered inside the manuscript
to explain the absorption and emission spectroscopy. The remaining structures appear to be at
a much higher energy and they are not feasible in hydrocarbon solution, though in other
solvents as for example basic solvents such as dimethylsulfoxide may stabilize the open species
(those species with electronic energy of 16.5 and 14.5 kcal/mol), it is proven that the basic
solvents can break the intramolecular hydrogen bond, as well as the acid solvents such as
methanol (Catalán J. and J. C. del Valle (1993) Toward the Photostability Mechanism of
Intramolecular Hydrogen Bond Systems. The Photophysics of 1'-Hydroxy-2'-acetonaphthone. J.
Am. Chem. Soc. 115, 4321-4325).
H
O
CH3
N
108.7
CH3
O
105.4
CH3
N
H
CH3
88.4
86.3
83.3
E
kcal/mol
75.0
15.1
H
O
CH3
14.5
N
13.6
CH3
10.7
O
CH3
N
CH3
H
0.9
O
H
N
CH3
0.0
O
CH3
H
N
CH3
CH3
Figure S3. Ground electronic-state energies and Franck-Condon state energies for some of the
isomers studied referred to the NH-tautomers as origin. The calculations have been executed
at the DFT-B3LYP level with 6-31G** basis set and full geometry optimization and at the TDDFT single point calculations with 6-31G** basis set. The OH-tautomer molecule with state
energy 0.9 kcal/mol and the NH-tautomers with state energies of 0.0 kcal/mol are considered
inside the manuscript to explain the absorption and emission spectroscopy.
Figure S4. Normalized fluorescence excitation and emission spectra of 1 in cyclohexane
together with the absorption spectra. (Cf. A. Brenlla, F. Rodríguez-Prieto, M. Mosquera,
M. A. Ríos, M. C. Ríos Rodríguez. J. Phys. Chem. A 2009, 113, 56-67.)
Figure S5. Fluorescence and absorption bands of MHN at room temperature in
cyclohexane solution (cf. J. Catalán, J. C. del Valle, J. Palomar, C. Díaz, J. L.G. de Paz.
J. Phys. Chem. A. 1999, 103, 10921-10934). This figure depicts an approximate mirror
image symmetry between the absorption (right) and the fluorescence (left) bands.
1
A
F
24,5
25,0
Intensity
24,0
Fluorescence
0
Absorption
20
30
-1
Wavenumber (kK) (1 kK= 1000 cm )
Figure S6. Fluorescence and absorption band of HAN at low temperature (77 K, black)
in 2-methylbutane (cf. J.Catalán, J.L.G. de Paz. J. Phys. Chem. A. 2008, 112, 904-914).
The black spectrum for absorption simulates the exact mirror image emission to be
compared with the real absorption at 77 K (in blue). The inset indicates the close mirror
image symmetry found for the real absorption and emission bands near the cross-point.
O14
H3
9
1H
H 10
H19
4
2
6
7
8
5
H 12
13
16
18
H 26
C H 27
N20 22 H 28
15
H 23
C H 24
H 25
H 17
H 11
Geometry for the OH normal tautomer with alternate hydrogens, that is, with the H28 and H27
hydrogens in alternate position to the H23 hydrogen.
Standard orientation:
---------------------------------------------------------------------
Center
Atomic
Number
Atomic
Number
Type
Coordinates (Angstroms)
X
Y
Z
--------------------------------------------------------------------1
1
0
-4.233587 -2.217807 -0.000125
2
6
0
-3.569742 -1.358414 -0.000075
3
1
0
-1.770685 -2.534867 -0.000128
4
6
0
-2.202964 -1.540772 -0.000076
5
6
0
-3.280562 1.047223 0.000039
6
6
0
-1.329465 -0.425542 -0.000019
7
6
0
-4.111692 -0.052994 -0.000020
8
6
0
-1.870689 0.895029 0.000050
9
6
0
0.096026 -0.603693 -0.000032
10
1
0
-5.189649 0.082019 -0.000024
11
1
0
-1.397184 3.014234 0.000155
12
1
0
-3.696619 2.051282 0.000081
13
6
0
0.957497 0.515244 0.000046
14
8
0
0.557413 -1.851586 -0.000034
15
6
0
2.415269 0.326532 -0.000041
16
6
0
0.371758 1.817661 0.000121
17
1
0
1.021169 2.686201 0.000160
18
6
0
-0.983458 2.010195 0.000114
19
1
0
1.580172 -1.758658 0.000222
20
7
0
2.871110 -0.888167 0.000155
21
6
0
3.303498 1.553862 -0.000287
22
6
0
4.293297 -1.193039 0.000100
23
1
0
4.361113 1.293948 -0.000139
24
1
0
3.104077 2.172227 0.880664
25
1
0
3.104213 2.171849 -0.881533
26
1
0
4.415935 -2.278453 -0.000548
27
1
0
4.805509 -0.800497 0.888180
28
1
0
4.805809 -0.799387 -0.887306
--------------------------------------------------------------------Dipole moment (field-independent basis, Debye):
X=
2.3443 Y=
1.7488 Z=
0.0000 Tot=
2.9247
Exact polarizability: 256.323 2.057 158.222 0.003 0.001 59.714
Thermodynamic Data values:
Zero-point correction=
0.229553 (Hartree/Particle)
Thermal correction to Energy=
0.242363
Thermal correction to Enthalpy=
0.243307
Thermal correction to Gibbs Free Energy=
Sum of electronic and zero-point Energies=
Sum of electronic and thermal Energies=
Sum of electronic and thermal Enthalpies=
Sum of electronic and thermal Free Energies=
0.190548
-632.994128
-632.981318
-632.980374
-633.033134
O14
H3
H19
9
1H
4
2
6
7
8
16
18
5
H 10
13
H 12
H 26
C H 27
N20 22 H 28
15
H 23
C H 24
H 25
H 17
H 11
Geometry for the NH proton-transferred tautomer with alternate hydrogens, that is, with the
H28 and H27 hydrogens in alternate position to the H23 hydrogen.
Standard orientation:
--------------------------------------------------------------------Center
Atomic
Number
Atomic
Number
Type
Coordinates (Angstroms)
X
Y
Z
--------------------------------------------------------------------1
1
0
4.254804 -2.221076 -0.000172
2
6
0
3.590715 -1.361746 -0.000110
3
1
0
1.774978 -2.532197 -0.000224
4
6
0
2.217215 -1.541858 -0.000146
5
6
0
3.285002 1.040617 0.000108
6
6
0
1.348136 -0.435255 -0.000051
7
6
0
4.124900 -0.060447 0.000025
8
6
0
1.881378 0.881432 0.000066
9
6
0
-0.106169 -0.659118 -0.000025
10
1
0
5.202135 0.081992 0.000047
11
1
0
1.407784 3.009260 0.000330
12
1
0
3.699557 2.045509 0.000199
13
6
0
-0.963887 0.518841 -0.000066
14
8
0
-0.560643 -1.840112 -0.000035
15
6
0
-2.373112 0.366531 -0.000073
16
6
0
-0.360657 1.825291 0.000065
17
1
0
-1.003593 2.699749 0.000247
18
6
0
0.987033 2.008052 0.000164
19
1
0
-2.151676 -1.591545 0.000543
20
7
0
-2.899193 -0.859012 0.000128
21
6
0
-3.292828 1.563329 -0.000368
22
6
0
-4.305710 -1.214709 0.000211
23
1
0
-4.343991 1.277159 -0.003096
24
1
0
-3.109002 2.186805 -0.880127
25
1
0
-3.112850 2.184125 0.882149
26
1
0
-4.375094 -2.303678 0.000355
27
1
0
-4.827854 -0.844088 -0.889495
28
1
0
-4.827811 -0.843794 0.889821
--------------------------------------------------------------------Rotational constants (GHZ):
1.4811399
0.3725393
0.2987813
Dipole moment (field-independent basis, Debye):
X= -4.0655 Y=
1.7856 Z=
0.0009 Tot=
4.4404
Exact polarizability: 274.181 -1.621 156.147 -0.004 0.007 59.516
Thermodynamical Data:
Zero-point correction=
Thermal correction to Energy=
Thermal correction to Enthalpy=
0.230181 (Hartree/Particle)
0.243124
0.244069
Thermal correction to Gibbs Free Energy=
0.190918
Sum of electronic and zero-point Energies=
-632.995275
Sum of electronic and thermal Energies=
-632.982332
Sum of electronic and thermal Enthalpies=
-632.981387
Sum of electronic and thermal Free Energies=
O14
H3
-633.034538
H19
N22 24 H 25
9
1H
15 21
4
2
6
7
8
C H 20
H19 H 23
13
16
18
5
H 10
H 12
H 27
C H 28
H 17
H 11
NH tautomer with eclipsed hydrogens, that is, with the H25 and H28 hydrogens in eclipsed
position to the H23 and H20 hydrogens.
Standard orientation:
--------------------------------------------------------------------Center
Atomic
Number
Atomic
Number
Type
Coordinates (Angstroms)
X
Y
Z
--------------------------------------------------------------------1
1
0
4.250937 -2.228193 -0.011366
2
6
0
3.590865 -1.365792 -0.007289
3
1
0
1.769813 -2.527668 -0.006687
4
6
0
2.216652 -1.539448 -0.004892
5
6
0
3.296487 1.038030 0.000943
6
6
0
1.352902 -0.428404 -0.000145
7
6
0
4.131170 -0.066943 -0.004272
8
6
0
1.892361 0.884660 0.003002
9
6
0
-0.102422 -0.646504 0.002839
10
1
0
5.209086 0.070298 -0.005915
11
1
0
1.424226 3.013097 0.016315
12
1
0
3.715324 2.041131 0.003527
13
6
0
-0.963099 0.534689 -0.000076
14
8
0
-0.554564 -1.827552 0.006531
15
6
0
-2.371722 0.369269 -0.005506
16
6
0
-0.346989 1.836899 0.007244
17
1
0
-0.976243 2.720142 0.017859
18
6
0
1.000989 2.012971 0.009216
19
1
0
-2.868960 2.481239 -0.134856
20
1
0
-4.068437 1.394489 -0.835841
21
6
0
-3.350924 1.514907 -0.017397
22
7
0
-2.888735 -0.862132 0.006907
23
1
0
-3.926792 1.533207 0.915279
24
6
0
-4.297942 -1.199240 0.003010
25
1
0
-4.830019 -0.760135 0.855114
26
1
0
-2.143048 -1.594643 0.012006
27
1
0
-4.388183 -2.284433 0.070583
28
1
0
-4.800008 -0.873764 -0.916673
--------------------------------------------------------------------Rotational constants (GHZ):
1.4938573
0.3706052
Dipole moment (field-independent basis, Debye):
X= -4.0278 Y=
1.6908 Z=
0.0062 Tot=
4.3683
0.2980473
Exact polarizability: 275.697 -1.629 154.753 -0.038 0.296 59.267
Thermodynamical Data:
Zero-point correction=
0.229767 (Hartree/Particle)
Thermal correction to Energy=
0.242919
Thermal correction to Enthalpy=
0.243863
Thermal correction to Gibbs Free Energy=
0.189025
Sum of electronic and zero-point Energies=
-632.995601
Sum of electronic and thermal Energies=
-632.982449
Sum of electronic and thermal Enthalpies=
-632.981505
Sum of electronic and thermal Free Energies=
O14
H3
9
1H
H 10
H19
6
7
8
5
H 12
H 27
C H 28
N22 24 H 25
15 21
4
2
-633.036343
13
16
18
C H 20
H19 H 23
H 17
H 11
NH tautomer possessing an intramolecular hydrogen bond in the ground state, and a fixed
dihedral angle of 20º (C9, C13, C15, N22). The methyl groups are not really in alternate
position but in an intermediate position between alternate and eclipsed –see the pictures
below.
Plots of the hydrogen-bonded non planar NH tautomer at different orientations obtained from
the standard orientation geometry (N is in blue, O is in red):
Standard orientation:
--------------------------------------------------------------------Center
Atomic
Number
Atomic
Number
Type
Coordinates (Angstroms)
X
Y
Z
--------------------------------------------------------------------1
1
0
-4.238080 -2.227403 0.226323
2
6
0
-3.580202 -1.366770 0.149208
3
1
0
-1.759637 -2.529401 0.101866
4
6
0
-2.207518 -1.541760 0.083252
5
6
0
-3.289520 1.033802 0.013901
6
6
0
-1.346722 -0.432925 -0.011416
7
6
0
-4.121549 -0.069103 0.112049
8
6
0
-1.886889 0.879790 -0.046665
9
6
0
0.106414 -0.653300 -0.096121
10
1
0
-5.198286 0.069161 0.159435
11
1
0
-1.425389 3.005231 -0.194366
12
1
0
-3.709752 2.035861 -0.016678
13
6
0
0.963648 0.529670 -0.144311
14
8
0
0.562073 -1.830869 -0.130099
15
6
0
2.360814 0.369014 0.024041
16
6
0
0.348999 1.832169 -0.166617
17
1
0
0.982863 2.709502 -0.246092
18
6
0
-0.999022 2.007645 -0.144458
19
1
0
3.914141 1.761766 -0.530012
20
1
0
2.758345 2.402821 0.651253
21
6
0
3.294235 1.509912 0.338881
22
7
0
2.910150 -0.833400 -0.179146
23
1
0
3.974351 1.228045 1.149015
24
6
0
4.298789 -1.185107 0.049141
25
1
0
4.975747 -0.540950 -0.521013
26
1
0
2.180251 -1.571574 -0.274129
27
1
0
4.448568 -2.212930 -0.285204
28
1
0
4.580381 -1.127602 1.109112
--------------------------------------------------------------------Rotational constants (GHZ):
1.4832213
0.3716685
0.2998388
Dipole moment (field-independent basis, Debye):
X=
3.9598 Y=
1.7145 Z=
0.4769 Tot=
4.3413
Exact polarizability: 275.787 1.654 154.860 -1.573 -2.122 60.620
Thermodynamical Data:
Zero-point correction=
0.230171 (Hartree/Particle)
Thermal correction to Energy=
0.243127
Thermal correction to Enthalpy=
0.244071
Thermal correction to Gibbs Free Energy=
Sum of electronic and zero-point Energies=
Sum of electronic and thermal Energies=
Sum of electronic and thermal Enthalpies=
Sum of electronic and thermal Free Energies=
0.190894
-632.992753
-632.979797
-632.978853
-633.032030