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Supporting Information
© Copyright Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, 2008
1
Synthesis and Photoinduced Electron Transfer Properties of
Phthalocyanine-[60]Fullerene Conjugates
Maurizio Quintiliani,[a] Axel Kahnt,[b] Thorsten Wölfle,[c] Wolfgang Hieringer,* [c] Purificación
Vázquez,[a] Andreas Görling,[c] Dirk M. Guldi,* [b] and Tomás Torres.*[a]
[a]Departamento de Química Orgánica (C-I), Facultad de Ciencias, Universidad Autónoma de Madrid, Cantoblanco, 28049 Madrid, Spain.
[b]Institute for Physical and Theoretical Chemistry, Friedrich-Alexander-Universität Erlangen-Nürnberg, 91058 Erlangen, Germany.
[c]Institute for Physical and Theoretical Chemistry, Friedrich-Alexander-Universität Erlangen-Nürnberg, 91058 Erlangen, Germany.
S1
2
Contents list
Figure S1. Fluorescence spectrum for 3 in THF excited at 610 nm Page S4
Figure S2 and S3. Differential absorption spectra (visible and near-infrared) of 3
in nitrogen saturated THF Pages S5 y S6
Figure S4. Time-absorption profile of the ZnPc triplet at 500 nm Page S7
Figure S5. Differential absorption spectra (visible and near-infrared) of 1b in
nitrogen saturated anisole Page S8
Figure S6. Differential absorption spectra (visible and near-infrared) of 1c in
nitrogen saturated anisole Page S9
Figure S7. Differential absorption spectra (visible and near-infrared) of 2 in
nitrogen saturated anisole Page S10
Figure S8. Time absorption profiles of the ZnPc radical cation band at 845 nm for
1b in different solvents Page S11
Figure S9. Time absorption profiles of the ZnPc radical cation band at 845 nm for
1c in different solvents Page S12
Figure S10. Time absorption profiles of the ZnPc radical cation band at 845 nm
for 2 in different solvents Page S13
Figure S11. 1H NMR spectrum for 5 in [D6]DMSO Page S14
Figure S12. MS and HR-MS spectra for 5 Pages S15 y S16
Figure S13. 1H NMR spectrum for 6 in [D6]DMSO Page S17
Figure S14. IR spectrum for 6 Page S18
Figure S15. MS and HR-MS spectra for 6 Pages S19 y S20
Figure S16. 1H NMR spectrum for 7 in [D6]DMSO Page S21
Figure S17. IR spectrum for 7 Page S22
Figure S18. MS and HR-MS spectra for 7 Pages S23 y S24
Figure S19. 1H NMR spectrum for 8 in [D6]acetone Page S25
Figure S20. IR spectrum for 8 Page S26
Figure S21. MS and HR-MS spectra for 8 Pages S27 y S28
Figure S22. 1H NMR spectrum for 1a in [D8]THF Page S29
Figure S23. MS spectrum for 1a Pages S30 y S31
Figure S24. 1H NMR spectrum for 1b in [D8]THF Page S32
3
Figure S25. MS spectrum for 1b Pages S33 y S34
Figure S26. 1H NMR spectrum for 1c in [D8]THF Page S35
Figure S27. MS spectrum for 1c Pages S36 y S37
Figure S28. UV/Vis spectrum for 3 in THF Page S38
Computational Details. Table 1 to Table 16 Pages S39 a S65
S2 y S3
4
Figure S1. Fluorescence spectrum of 3 in THF.
S4
5
Figure S2. Differential absorption spectra (visible and near-infrared) obtained upon femtosecond flash photolysis (670 nm) of
3 in nitrogen saturated THF with several time delays (i.e., 1 ps – black; 102 ps – red; 2892 ps – green) at room temperature.
S5
6
Figure S3. Differential absorption spectra (visible and near-infrared) obtained upon femtosecond flash photolysis (670 nm) of
3 in nitrogen saturated THF after 1.2 µs at room temperature.
S6
7
Figure S4. time-absorption profile of the ZnPc triplet at 500 nm, monitoring the recovery of the singlet ground state in the
absence of molecular oxygen (i.e., black time-absorption profile) and in the presence of molecular oxygen (i.e., red time-
absorption profile).
S7
8
Figure S5. Differential absorption spectra (visible and near-infrared) obtained upon femtosecond flash photolysis (670 nm) of
1b in nitrogen saturated anisole with several time delays (i.e., 1 ps – black; 102 ps – red; 2892 ps – green) at room temperature.
S8
9
Figure S6. Differential absorption spectra (visible and near-infrared) obtained upon femtosecond flash photolysis (670 nm) of
1c in nitrogen saturated anisole with several time delays (i.e., 1 ps – black; 102 ps – red; 2892 ps – green) at room temperature.
S9
10
Figure S7. Differential absorption spectra (visible and near-infrared) obtained upon femtosecond flash photolysis (670 nm) of
2 in nitrogen saturated anisole with several time delays (i.e., 1 ps – black; 102 ps – red; 2892 ps – green) at room temperature.
S10
11
Figure S8. Time absorption profiles of the ZnPc radical cation band at 845 nm for 1b in anisole (green line), in THF (red line)
and in benzonitrile (black line).
S11
12
Figure S9. Time absorption profiles of the ZnPc radical cation band at 845 nm for 1c in anisole (green line), in THF (red line)
and in benzonitrile (black line).
S12
13
Figure S10. Time absorption profiles of the ZnPc radical cation band at 845 nm for 2 in anisole (green line), in THF (red line)
and in benzonitrile (black line).
S13
14
Figure S11. 1H NMR spectrum for 5 in [D6]DMSO
¡Error! No se pueden crear objetos modificando códigos de campo.
S14
15
Figure S12. MS and HR-MS spectra for 5
16
S15 y S16
17
Figure S13. 1H NMR spectrum for 6 in [D6]DMSO
¡Error! No se pueden crear objetos modificando códigos de campo.
S17
18
Figure S14. IR spectrum for 6
600110016002100260031003600
cm-1
Tran
smitt
ance
1658
1611
S18
19
Figure S15. MS and HR-MS spectra for 6
20
S19 y S20
21
Figure S16. 1H NMR spectrum for 7 in [D6]DMSO
N
NN
N
N
NN N
Zn
t-Bu
t-Bu
t-BuCHO
7
S21
22
Figure S17. IR spectrum for 7
600110016002100260031003600
cm-1
Tran
smitt
ance
1677
1607
S22
23
Figure S18. MS and HR-MS spectra for 7
24
S23 y S24
25
Figure S19. 1H NMR spectrum for 8 in [D6]acetone
¡Error! No se pueden crear objetos modificando códigos de campo.
S25
26
Figure S20. IR spectrum for 8
600110016002100260031003600
cm-1
Tran
smitt
ance
1720
16771613
S26
27
Figure S21. MS and HR-MS spectra for 8
28
S27 y S28
29
Figure S22. 1H NMR spectrum for 1a in [D8]THF
¡Error! No se pueden crear objetos modificando códigos de campo.
N-CH3Pc
Pyrrolidine-H
S29
30
Figure S23. MS spectrum for 1a
31
S30 y S31
32
Figure S24. 1H NMR spectrum for 1b in [D8]THF
¡Error! No se pueden crear objetos modificando códigos de campo.
N-CH3Pc
Pyrrolidine-H
Vinyl-H
S32
33
Figure S25. MS spectrum for 1b
34
S33 y S34
35
Figure S26. 1H NMR spectrum for 1c in [D8]THF
¡Error! No se pueden crear objetos modificando códigos de campo.
Pc
Pyrrolidine-H
N-CH3
S35
36
Figure S27. MS spectrum for 1c
37
S36 y S37
38
Figure S28. UV/Vis spectrum for 3 in THF
¡Error! No se pueden crear objetos modificando códigos de campo.
0
50000
100000
150000
400 600 800 1000
ε
/ M-1 cm-1
Wavelength / nm
S38
39
Computational Details: Density-functional theory (DFT)1 calculations have been used to compute the ground state electronic
structure and geometries of the 2 zinc phthalocyanine fullerene conjugate and its building block molecules zinc phthalocyanine
(ZnPc) and methyl pyridyl fullerene (C60) along with their radical cations or anions, ZnPc•+ and C60•–. The gradient-corrected
exchange-correlation functional due to Becke2a and Perdew2b (hereafter denoted BP) has been used throughout in combination
with a standard split-valence basis set of valence triple-zeta quality (TZVP basis set as included in the TURBOMOLE3 package).
Geometry optimizations have been performed without any symmetry assumptions except for the zinc phthalocyanine (ZnPc),
where D4h symmetry has been assumed. The radical ions have been computed as spin doublets, and the S2 expectation values
where checked to be below 0.77.
Electronic excitation energies and intensities have been computed using time-dependent density-functional theory (TDDFT)4
within the adiabatic approximation and using the adiabatic exchange-correlation kernel from the BP functional. The same
valence triple zeta basis sets as for the ground state calculations were used. Previous studies on metal phthalocyanine
molecules have shown that the effect of a further augmentation of basis sets by inclusion of diffuse functions should be minor.5
In general, only the most intensive excitations are discussed in the present work, although up to 300 of the lowest electronic
excitations have been computed to cover the wavelength range of the experimental UV/Vis spectra (ca. 300 nm to 1200 nm).
To generate plots of simulated UV/Vis absorption spectra from the TDDFT data a Lorentzian broadening of the computed
excitation lines with a constant full width at half maximum of 25 nm has been used. For these plots, all computed excitations
form the TDDFT calculations have been included. All DFT and TDDFT calculations have been performed using the resolution
of the identity (RI) technique6 as implemented in the TURBOMOLE program package.3
S39
40
Table S1: Most intensive excitations of the ZnPc isolated fragment between 330 nm and 1200 nm.
Excit. label λ/[nm] ∆E/[eV] Osc. Str. Orbital transition
1Eu / "Q band" 633 1.96 0.65 2a1u → 7eg (91%)
4Eu / "B1 band" 400 3.10 0.33 2b1u → 7eg (75%)
5Eu 367 3.38 0.06 2a1u → 8eg (68%)
6Eu 361 3.43 0.75 1a1u → 7eg (30%)
7Eu / "B2 band" 329 3.76 0.95 1a1u → 7eg (57%)
S40
41
Table S2: Selected electronic excitations computed for the C60 isolated fragment between 250 nm and 1200 nm.
Excit. label λ/[nm] ∆E/[eV] Osc. Str. Orbital transition
40A 423 2.93 0.033 a 196a → 202a (37%)
147A 276 4.50 0.084 b σ/π → π*
148A 276 4.50 0.083 b π → π*
149A 274 4.53 0.018 b σ → π* (LUMO)
156A 270 4.59 0.077 b σ/π → π* (LUMO)
157A 269 4.60 0.003 b π → π*
a): see text; b): (predominantly) centered on the fullerene sphere (no illustration).
S41
42
Table S3: Selected electronic excitations computed for the ZnPc-C60 conjugate 2 between 330nm and 1200nm. "F→F" flags
transitions which are predominantly centered on the MepyC60, all other excitations are centered on the ZnPc moiety; "Mix"
signals that the involved orbitals are located on both ZnPc and MepyC60 to some extent; labels "Q" / "S" / "B1" / "B2" mark
excitations assigned to the Q / Soret / B1 / B2 bands in the ZnPc spectrum, respectively. Charge transfer excitations are not
included.
Excit. label λ/[nm] ∆E/[eV] Osc. Str. Orbital transition
17A (Q) 642 1.93 0.373 342a → 346a (73%)
19A (Q) 633 1.96 0.195 342a → 347a (57%)
118A 413 3.00 0.051 330a → 346a (48%)
119A 412 3.01 0.049 330a → 347a (52%)
126A (B1) 405 3.06 0.217 326a → 346a (49%)
131A (B1) 402 3.09 0.099 326a → 347a (50%)
180A (S, Mix) 366 3.39 0.103 342a → 361a (29%)
191A (Mix) 357 3.47 0.019 341a → 353a (64%)
194A (F→F) 355 3.49 0.024 335a → 351a (59%)
235A (F→F, Mix) 332 3.73 0.197 338a → 354a (19%)
239A (B2) 330 3.76 0.344 315a → 347a (45%)
S42
43
Table S4: Most intensive excitations computed for the C60•– radical anion at excitation wavelengths above 400 nm.
Excit. label λ/[nm] ∆E/[eV] Osc. Str. Orbital transition
4A 989 1.25 0.017 197a → 200a (93%)
10A 809 1.53 0.015 197a → 203a (81%)
37A 546 2.27 0.007 197a → 207a (58%)
S43
44
Table S5: Selected electronic excitations computed for the ZnPc•+ radical cation at excitation wavelengths above 400 nm.
Excit. label λ/[nm] ∆E/[eV] Osc. Str. Orbital transition
10A 696 1.78 0.287 α: 147a → 148a (47%)
11A 696 1.78 0.287 α: 147a → 149a (47%)
54A 421 2.94 0.267 β: 138a → 148a (27%)
55A 421 2.94 0.267 β: 138a → 149a (27%)
29A 472 2.63 0.017 α: 141a → 148a (48%)
30A 472 2.63 0.017 α: 141a → 149a (48%)
39A 455 2.72 0.01 α: 138a → 148a (47%)
40A 455 2.72 0.01 α: 138a → 149a (47%)
a): spin α = majority spin channel, spin β = minority spin channel
Note: The computed excitation spectrum of the ZnPc-C60 conjugate 2 features various excitations which are of charge-
transfer type, i. e. excitations which are (dominantly) assigned to transitions from an occupied orbital which is located on the
ZnPc moiety to a virtual orbital which is located on the fullerene and vice versa. Within the computational approach used in
the present work, the excitation energies associated with these charge transfer transitions must be considered unreliable,7 and
their discussion is therefore omitted. This includes the HOMO → LUMO transition of the ZnPc-MepyC60 conjugate, which is
of charge transfer character and has only low intensity.
(Complete lists of the computed excitation energies of ZnPc, ZnPc•+, MepyC60, C60•–, and ZnPc-C60 can be obtained from the
authors upon request.)
S44
45
Table S6: Cartesian coordinates of optimized geometries and total energies of ZnPc
57
Energy = -3447.514223960
Zn 0.0000000 0.0000000 0.0000000
C 5.3978231 1.4273594 0.0000000
C 4.2003149 0.7080189 0.0000000
C 4.2003149 -0.7080189 0.0000000
C 5.3978231 -1.4273594 0.0000000
C 6.5937971 -0.7044017 0.0000000
C 6.5937971 0.7044017 0.0000000
C 2.7980638 1.1268964 0.0000000
N 2.0037954 0.0000000 0.0000000
C 2.7980638 -1.1268964 0.0000000
N 2.4005352 2.4005352 0.0000000
C 1.1268964 2.7980638 0.0000000
C 0.7080189 4.2003149 0.0000000
C -0.7080189 4.2003149 0.0000000
C -1.1268964 2.7980638 0.0000000
N 0.0000000 2.0037954 0.0000000
C 1.4273594 5.3978231 0.0000000
C 0.7044017 6.5937971 0.0000000
C -0.7044017 6.5937971 0.0000000
C -1.4273594 5.3978231 0.0000000
N -2.4005352 2.4005352 0.0000000
C -2.7980638 1.1268964 0.0000000
C -4.2003149 0.7080189 0.0000000
C -4.2003149 -0.7080189 0.0000000
C -2.7980638 -1.1268964 0.0000000
N -2.0037954 0.0000000 0.0000000
C -5.3978231 1.4273594 0.0000000
C -6.5937971 0.7044017 0.0000000
C -6.5937971 -0.7044017 0.0000000
46
C -5.3978231 -1.4273594 0.0000000
N -2.4005352 -2.4005352 0.0000000
C -1.1268964 -2.7980638 0.0000000
C -0.7080189 -4.2003149 0.0000000
C 0.7080189 -4.2003149 0.0000000
C 1.1268964 -2.7980638 0.0000000
N 0.0000000 -2.0037954 0.0000000
C 1.4273594 -5.3978231 0.0000000
C 0.7044017 -6.5937971 0.0000000
C -0.7044017 -6.5937971 0.0000000
C -1.4273594 -5.3978231 0.0000000
N 2.4005352 -2.4005352 0.0000000
H 2.5178099 5.3898774 0.0000000
H 1.2376443 7.5460618 0.0000000
H -1.2376443 7.5460618 0.0000000
H -2.5178099 5.3898774 0.0000000
H -5.3898774 2.5178099 0.0000000
H -5.3898774 -2.5178099 0.0000000
H -7.5460618 1.2376443 0.0000000
H -7.5460618 -1.2376443 0.0000000
H 5.3898774 2.5178099 0.0000000
H 5.3898774 -2.5178099 0.0000000
H 7.5460618 1.2376443 0.0000000
H 7.5460618 -1.2376443 0.0000000
H -2.5178099 -5.3898774 0.0000000
H 2.5178099 -5.3898774 0.0000000
H -1.2376443 -7.5460618 0.0000000
H 1.2376443 -7.5460618 0.0000000
S45 y S46
47
Table S7: Cartesian coordinates of optimized geometries and total energies of ZnPc•+:
57
Energy = -3447.277037257
Zn 0.0000001 0.0000000 0.0000377
C 5.3923629 1.4284559 0.0000034
C 4.2009618 0.7069178 0.0000305
C 4.2009616 -0.7069179 0.0000284
C 5.3923631 -1.4284557 -0.0000014
C 6.5933782 -0.7014591 -0.0000365
C 6.5933783 0.7014594 -0.0000344
C 2.7955228 1.1252504 0.0000368
N 1.9981191 0.0000002 0.0000366
C 2.7955227 -1.1252502 0.0000335
N 2.3994574 2.3994573 0.0000371
C 1.1252503 2.7955222 0.0000392
C 0.7069177 4.2009613 0.0000347
C -0.7069179 4.2009610 0.0000347
C -1.1252501 2.7955219 0.0000393
N 0.0000002 1.9981179 0.0000396
C 1.4284558 5.3923624 -0.0000007
C 0.7014591 6.5933777 -0.0000471
C -0.7014592 6.5933775 -0.0000474
C -1.4284559 5.3923625 -0.0000007
N -2.3994573 2.3994570 0.0000373
C -2.7955227 1.1252501 0.0000370
C -4.2009617 0.7069177 0.0000308
C -4.2009616 -0.7069180 0.0000286
C -2.7955226 -1.1252504 0.0000337
N -1.9981190 -0.0000001 0.0000368
C -5.3923628 1.4284558 0.0000038
C -6.5933782 0.7014595 -0.0000341
C -6.5933782 -0.7014590 -0.0000372
48
C -5.3923632 -1.4284558 -0.0000015
N -2.3994573 -2.3994574 0.0000304
C -1.1252502 -2.7955223 0.0000311
C -0.7069177 -4.2009613 0.0000237
C 0.7069179 -4.2009612 0.0000236
C 1.1252502 -2.7955221 0.0000311
N -0.0000001 -1.9981179 0.0000337
C 1.4284558 -5.3923627 -0.0000042
C 0.7014590 -6.5933777 -0.0000392
C -0.7014593 -6.5933778 -0.0000390
C -1.4284559 -5.3923625 -0.0000039
N 2.3994573 -2.3994571 0.0000303
H 2.5185487 5.3877842 0.0000085
H 1.2357233 7.5442422 -0.0000849
H -1.2357235 7.5442421 -0.0000864
H -2.5185488 5.3877842 0.0000090
H -5.3877843 2.5185488 0.0000128
H -5.3877850 -2.5185487 0.0000034
H -7.5442422 1.2357245 -0.0000627
H -7.5442423 -1.2357240 -0.0000691
H 5.3877845 2.5185488 0.0000123
H 5.3877848 -2.5185487 0.0000033
H 7.5442423 1.2357244 -0.0000637
H 7.5442423 -1.2357241 -0.0000671
H -2.5185488 -5.3877841 0.0000022
H 2.5185487 -5.3877845 0.0000018
H -1.2357236 -7.5442423 -0.0000674
H 1.2357232 -7.5442423 -0.0000680
S47 y S48
49
Table S8: Cartesian coordinates of optimized geometries and total energies of C60:
71
Energy = -2460.351003198
C -1.9019683 0.7383166 -2.5562686
C -1.9019712 -0.7387488 -2.5561547
C -2.4538696 -1.4368555 -1.4967384
C -3.3294151 0.8017201 -0.4207056
C -2.4538614 1.4365903 -1.4969581
C -0.6530944 1.1772320 -3.1466910
C 0.1175030 -0.0002873 -3.5087504
C -0.6530889 -1.1777521 -3.1465018
C 0.0039604 -2.3181182 -2.6593135
C -1.7620835 -2.5835608 -0.9703285
C -2.7215782 -1.4362614 0.8334420
C -2.4049433 -0.7386154 1.9847853
C -2.4049494 0.7389288 1.9846668
C -2.7216018 1.4363948 0.8332172
C -1.9245700 2.5813588 0.4716924
C -1.7620871 2.5833853 -0.9707412
C -0.5653806 3.0392526 -1.5447309
C 0.0039513 2.3176855 -2.6596865
C 1.5101177 -0.0002707 -3.3727494
C 2.1880758 1.1778699 -2.8517866
C 1.4479120 2.3143922 -2.5028194
C 1.7690991 3.0420620 -1.2842134
C 0.5209476 3.4935929 -0.6904015
C 0.3655334 3.4921866 0.6992512
C -0.8826657 3.0363945 1.2934701
C -0.5708562 2.3175375 2.5067289
C -1.3178215 1.1770870 2.8355436
C -1.9245621 -2.5812945 0.4721058
C 1.5175428 -1.1780340 3.1766862
C 0.8719037 -2.3147756 2.6730278
50
C 1.4528124 -3.0428223 1.5540589
C 2.6550320 -2.6071809 0.9837276
C 3.3234354 -1.4281084 1.5095373
C 2.7646533 0.7286940 2.5863486
C 1.5175350 1.1785543 3.1764936
C 0.7419328 0.0002891 3.5344461
C -0.6464527 0.0002718 3.3609980
C -1.3178159 -1.1766335 2.8357382
C -0.5708449 -2.3171333 2.5071084
C 0.3655525 -3.4920689 0.6998173
C 0.5209592 -3.4936969 -0.6898358
C 1.7691107 -3.0422620 -1.2837216
C 2.8152625 -2.6057768 -0.4630771
C 3.5827987 -1.4282707 -0.8292269
C 3.8982977 -0.6999331 0.3899289
C 3.8982937 0.7000089 0.3898141
C 3.3234309 1.4283647 1.5093056
C 0.8718911 2.3152146 2.6726528
C 1.4527997 3.0430858 1.5535686
C 2.6550255 2.6073517 0.9833029
C 2.8152533 2.6057098 -0.4634971
C 3.5827899 1.4281465 -0.8294572
C 3.2748530 0.7289725 -2.0025464
C 3.2748566 -0.7292873 -2.0024291
C 2.1880808 -1.1783236 -2.8515952
C 1.4479207 -2.3147917 -2.5024456
C -0.8826507 -3.0361942 1.2939625
C -0.5653694 -3.0395126 -1.5442408
C 2.7646563 -0.7282629 2.5864668
C -3.3294131 -0.8018033 -0.4205757
C -4.8775889 -1.1455096 -0.6318251
H -5.1702506 -2.0627456 -0.1058114
H -5.0322335 -1.2988565 -1.7113452
C -4.8775794 1.1453535 -0.6320940
51
H -5.0322006 1.2984072 -1.7116605
H -5.1702704 2.0627272 -0.1063419
N -5.6524124 -0.0000214 -0.1946081
C -6.0389641 0.0001552 1.2217941
H -6.6561741 0.8868651 1.4198675
H -6.6561118 -0.8865440 1.4201075
H -5.1917080 0.0002833 1.9315111
S49, S50 y S51
52
Table S9: Cartesian coordinates of optimized geometries and total energies of C60•–:
71
Energy = -2460.450345171
C -1.4184306 0.7358373 -2.5734803
C -1.4183696 -0.7360065 -2.5734531
C -1.9721192 -1.4409747 -1.5169410
C -2.8504135 0.8025334 -0.4418124
C -1.9721599 1.4406841 -1.5169019
C -0.1604330 1.1710719 -3.1623439
C 0.6047629 0.0000121 -3.5346583
C -0.1603324 -1.1711284 -3.1623253
C 0.4918364 -2.3145824 -2.6670397
C -1.2874300 -2.5878493 -0.9876542
C -2.2433391 -1.4399254 0.8140276
C -1.9287584 -0.7372992 1.9640154
C -1.9287922 0.7369432 1.9640133
C -2.2435717 1.4396010 0.8140952
C -1.4511986 2.5851697 0.4501150
C -1.2876875 2.5877161 -0.9876099
C -0.0810571 3.0422231 -1.5644181
C 0.4916441 2.3146243 -2.6670550
C 2.0128527 0.0000602 -3.3944767
C 2.6812084 1.1720169 -2.8644312
C 1.9416494 2.3118310 -2.5080778
C 2.2623201 3.0412210 -1.2978759
C 1.0083796 3.4828394 -0.7040230
C 0.8516616 3.4816629 0.6856574
C -0.4042445 3.0378074 1.2807274
C -0.0912753 2.3143873 2.4840800
C -0.8365810 1.1706536 2.8200076
C -1.4509457 -2.5854135 0.4500234
C 1.9989964 -1.1719883 3.1642295
C 1.3578341 -2.3122125 2.6522721
53
C 1.9406901 -3.0436205 1.5443359
C 3.1550194 -2.6121858 0.9713529
C 3.8158207 -1.4310032 1.4992465
C 3.2543926 0.7264302 2.5743609
C 1.9988959 1.1719013 3.1642278
C 1.2292069 -0.0000766 3.5316299
C -0.1747902 -0.0001241 3.3551606
C -0.8364812 -1.1709532 2.8199753
C -0.0910901 -2.3146127 2.4840077
C 0.8519449 -3.4816721 0.6855344
C 1.0086481 -3.4827176 -0.7041003
C 2.2625366 -3.0410911 -1.2979564
C 3.3157693 -2.6099470 -0.4684729
C 4.0792046 -1.4301172 -0.8366938
C 4.3943690 -0.7001784 0.3821850
C 4.3942676 0.7003816 0.3822025
C 3.8156357 1.4310938 1.4992513
C 1.3576499 2.3120852 2.6523336
C 1.9404455 3.0435578 1.5444149
C 3.1547549 2.6122002 0.9714150
C 3.3155428 2.6100594 -0.4683798
C 4.0790290 1.4303071 -0.8366242
C 3.7721836 0.7276976 -2.0093926
C 3.7722455 -0.7274706 -2.0094253
C 2.6812725 -1.1718383 -2.8644265
C 1.9417980 -2.3116599 -2.5080508
C -0.4039341 -3.0378802 1.2805721
C -0.0807682 -3.0421228 -1.5643986
C 3.2544782 -0.7263898 2.5743749
C -2.8504632 -0.8029564 -0.4417837
C -4.3885265 -1.1453221 -0.6555310
H -4.6814489 -2.0628975 -0.1287954
H -4.5464069 -1.2996866 -1.7349647
C -4.3883375 1.1449859 -0.6561714
54
H -4.5459268 1.2985857 -1.7357659
H -4.6812742 2.0630034 -0.1301704
N -5.1805578 0.0000300 -0.2227940
C -5.5241787 0.0005613 1.2049593
H -6.1354713 0.8886001 1.4214100
H -6.1352692 -0.8874249 1.4221462
H -4.6568830 0.0009519 1.8901143
S52, S53 y S54
55
Table S10: Cartesian coordinates of optimized geometries and total energies of ZnPc-C60 conjugate 2:
126
Energy = -5906.668683137
C -7.7621483 -5.1124100 -1.6220129
C -7.3102000 -3.8740517 -1.1596925
C -5.9997907 -3.7216678 -0.6445406
C -5.1203113 -4.8054118 -0.5836973
C -5.5761186 -6.0427175 -1.0468425
C -6.8796037 -6.1942726 -1.5591619
C -5.8628880 -2.3169961 -0.2576766
N -7.0479782 -1.6680147 -0.5347510
C -7.9483933 -2.5598463 -1.0773914
N -9.1981809 -2.3130188 -1.4736144
C -9.7937889 -1.1219958 -1.4037017
C -11.1665778 -0.8679215 -1.8425894
C -11.4211231 0.5046176 -1.6045224
C -10.1986316 1.0627030 -1.0248034
N -9.2611831 0.0565246 -0.9254139
C -12.1452032 -1.6954486 -2.3981655
C -13.3821671 -1.1245474 -2.7104788
C -13.6353460 0.2407796 -2.4737970
C -12.6585696 1.0717892 -1.9181867
N -10.0597736 2.3398760 -0.6662642
C -8.9528033 2.8624939 -0.1353730
C -8.8159543 4.2681198 0.2482658
C -7.5061118 4.4216777 0.7643728
C -6.8680276 3.1072054 0.6854424
N -7.7689831 2.2139712 0.1438802
C -9.6946126 5.3521333 0.1812555
C -9.2386748 6.5910678 0.6398828
C -7.9357558 6.7438529 1.1532733
C -7.0539410 5.6617094 1.2219212
N -5.6188600 2.8605172 1.0810229
56
C -5.0230354 1.6690291 1.0097504
C -3.6497162 1.4158259 1.4423268
C -3.3950762 0.0442389 1.2049378
C -4.6178999 -0.5160473 0.6298665
N -5.5556069 0.4898296 0.5327059
C -2.6666927 2.2368042 2.0015510
C -1.4293396 1.6686902 2.3048440
C -1.1649927 0.2982961 2.0692548
C -2.1586308 -0.5227322 1.5212447
N -4.7562612 -1.7941034 0.2723045
Zn -7.4085381 0.2732256 -0.1968809
C 0.1951395 -0.2849941 2.3816051
C 1.3067011 -0.0343633 1.2753625
C 2.6703048 -0.0610393 2.1310919
C 2.1644068 -0.2855754 3.5862623
N 0.8112464 0.2505874 3.5975165
C 1.0989251 1.2523606 0.4679159
C 0.5598702 0.9378818 -0.8291064
C 0.6464018 -0.4976351 -1.0231959
C 1.2414187 -1.0727966 0.1536570
C 2.1360367 -2.1190291 0.0165817
C 2.4351427 -2.6563633 -1.2955624
C 1.8199747 -2.1263714 -2.4402344
C 0.9016236 -1.0200904 -2.3004991
C 3.8429185 -3.0127565 -1.3331310
C 4.5857868 -2.8289436 -2.5041784
C 3.9500179 -2.2641474 -3.6849485
C 2.5922807 -1.9207550 -3.6525743
C 4.9074494 -1.3858983 -4.3305515
C 6.1392276 -1.4117145 -3.5520851
C 5.9427757 -2.3067807 -2.4279951
C 4.4762576 -0.1894350 -4.9174110
C 5.2558908 1.0258740 -4.7472435
C 6.4400325 1.0006268 -4.0003341
57
C 6.8918779 -0.2412427 -3.3936662
C 7.4778241 0.0762573 -2.1024663
C 7.3872310 1.5161223 -1.9096276
C 6.7457195 2.0863577 -3.0823523
C 5.8515131 3.1554113 -2.9409211
C 4.6187382 3.1815074 -3.7181625
C 4.3293612 2.1380164 -4.6070902
C 7.2905094 -0.7884277 -1.0174683
C 6.5081203 -2.0043720 -1.1823427
C 2.1435476 -0.6785901 -4.2650950
C 3.0688075 0.1703929 -4.8844635
C 2.9780155 1.6100340 -4.6918147
C 5.7399340 -2.2110060 0.0329057
C 4.4262362 -2.6996616 -0.0397083
C 1.0947935 -0.1208384 -3.4273805
C 3.3873119 -2.1455264 0.8043207
C 1.0083505 1.2623610 -3.2411317
C 0.7263605 1.8034311 -1.9203548
C 3.6799026 -1.1247992 1.6898571
C 1.4960160 3.0130775 -1.7517931
C 2.0606393 3.2948739 -0.4986167
C 1.8537521 2.3989623 0.6202886
C 3.1017292 2.3762867 1.4114179
C 3.5299786 1.2021994 1.9976779
C 4.9222336 0.8453970 1.9235881
C 5.0148841 -0.5906813 1.7322371
C 6.0417455 -1.1298997 0.9420468
C 5.8627974 1.6953504 1.3210024
C 5.4157260 2.9312890 0.7215447
C 4.0508783 3.2556265 0.7581593
C 3.4124376 3.8220030 -0.4172680
C 1.9659565 2.1456851 -3.8861605
C 2.2672783 3.2300478 -2.9628001
C 3.5715886 3.7353784 -2.8815902
58
C 4.1526742 4.0448374 -1.5834088
C 6.9148374 1.1365799 0.4856142
C 7.0037141 -0.2468549 0.3008092
C 5.5637986 3.6924896 -1.6244899
C 6.1828541 3.1468056 -0.4922200
C 7.1128878 2.0362658 -0.6389565
C 0.0866877 -0.0707202 4.8252408
H -11.9418248 -2.7515765 -2.5784077
H -14.1676256 -1.7448900 -3.1454563
H -14.6124755 0.6537295 -2.7299447
H -12.8476262 2.1295542 -1.7319914
H -10.7015444 5.2266445 -0.2182543
H -6.0438073 5.7724901 1.6175670
H -9.9009662 7.4575163 0.6007924
H -7.6120302 7.7259862 1.5019004
H -8.7723527 -5.2217051 -2.0178713
H -4.1122204 -4.6809264 -0.1868424
H -7.2026147 -7.1748408 -1.9128048
H -4.9128246 -6.9086199 -1.0131620
H -2.8666259 3.2921650 2.1904750
H -1.9767442 -1.5848820 1.3445858
H -0.6403956 2.2782379 2.7470237
H 0.0833574 -1.3918443 2.4581370
H 2.7993467 0.2204694 4.3269768
H 2.1757754 -1.3766905 3.8091172
H 0.0027079 -1.1667451 4.9916590
H 0.6109623 0.3719055 5.6834442
H -0.9244005 0.3533846 4.7835251
Note that the geometric relaxation of the charged fragments as compared to their uncharged counterparts is minor and
merely leads to a slight extension of the molecular dimensions due to the removal of an electron from a bonding molecular
orbital (ZnPc) or the addition of an electron to an antibonding molecular orbital (C60).
S55 – S59
59
Tables S11: HOMO and LUMO energies of ZnPc:
Total energy = -3447.5142239600 H = -93811.6885539 eV
HOMO-LUMO Separation
HOMO: 111. 2 a1u -0.18599005 H = -5.06105 eV
LUMO: 112. 7 eg -0.13363121 H = -3.63629 eV
Gap : +0.05235884 H = +1.42476 eV
Number of MOs= 668, Electrons= 294.00, Symmetry: d4h
S60
60
Tables S12: HOMO and LUMO energies of ZnPc•+:
Total energy = -3447.2770372570 H = -93805.2343716 eV
HOMO-LUMO Separation
HOMO: 293. a 147 a -0.29784568 H = -8.10480 eV
LUMO: 294. b 147 a -0.28829551 H = -7.84492 eV
Gap : +0.00955017 H = +0.25987 eV
Number of MOs= 1778, Electrons= 293.00, Symmetry: c1
S61
61
Tables S13: HOMO and LUMO energies of C60:
Total energy = -2460.3510031980 H = -66949.5952884 eV
HOMO-LUMO Separation
HOMO: 196. 196 a -0.20523287 H = -5.58467 eV
LUMO: 197. 197 a -0.15144175 H = -4.12094 eV
Gap : +0.05379113 H = +1.46373 eV
Number of MOs= 1258, Electrons= 392.00, Symmetry: c1
S62
62
Tables S14: HOMO and LUMO energies of C60•–:
Total energy = -2460.4503451710 H = -66952.2985226 eV
HOMO-LUMO Separation
HOMO: 393. a 197 a -0.04722462 H = -1.28505 eV
LUMO: 394. b 197 a -0.04252160 H = -1.15707 eV
Gap : +0.00470303 H = +0.12798 eV
Number of MOs= 2516, Electrons= 393.00, Symmetry: c1
S63
63
Tables S15: HOMO and LUMO energies of ZnPc-C60 conjugate 2:
Total energy = -5906.6686831370 H = -160728.7242043 eV
HOMO-LUMO Separation
HOMO: 342. 342 a -0.18888617 H = -5.13986 eV
LUMO: 343. 343 a -0.15029575 H = -4.08976 eV
Gap : +0.03859042 H = +1.05010 eV
Number of MOs= 2135, Electrons= 684.00, Symmetry: c1
S64
64
Table S16: Fluorescence quantum yields of the dyads following 610 nm photoexcitation.
1a 1b 1c 2
ΦFlu, THF 0.023 0.030 0.020 0.003
ΦFlu, anisole 6.14 x 10-3 9.56 x 10-3 1.30 x 10-3 0.0028
ΦFlu, toluole 0.025 0.025 8.63 x 10-3 0.0266
References [1] R. G. Parr, W. Yang, in Density-Functional Theory of Atoms and Molecules, Oxford University Press, New York, Oxford,
1989. [2] a) A. D. Becke, Phys. Rev. A 1988, 38, 3098; b) J. P. Perdew, Phys. Rev. B 1986, 33, 8822. [3] R. Ahlrichs, et al. TURBOMOLE versions 5.7 and 5.9, University of Karlsruhe, since 1988. [4] a) E. Runge, E. K. U. Gross, Phys. Rev. Lett. 1984, 52, 997; b) R. Bauernschmitt, R. Ahlrichs, Chem. Phys. Lett. 1996,
256, 454. [5] K. A. Nguyen, R. Pachter, J. Chem. Phys. 2001, 114, 10757. [6] a) K. Eichkorn, O. Treutler, H. Öhm, M. Häser, R. Ahlrichs, Chem. Phys. Lett. 1995, 240, 283; b) R. Bauernschmitt, M.
Häser, O. Treutler, R. Ahlrichs, Chem. Phys. Lett. 1997, 264, 573. [7] A. Dreuw, J. L. Weisman, M. Head-Gordon, J. Chem. Phys. 2003, 119, 2943.
S65