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

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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

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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

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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

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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

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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

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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