Supporting Information

© Copyright Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, 2008

1

p-Phenyleneethynylene Molecular Wires: Influence of Structure on

Photoinduced Electron-Transfer Properties

Mateusz Wielopolski,[a] Carmen Atienza,[a,b] Timothy Clark,[c] Dirk M. Guldi,[a]*

Nazario Martín[b,d]*

[a] Department of Chemistry and Pharmacy

Interdisciplinary & Center for Molecular Materials (ICMM)

Friedrich-Alexander-Universität Erlangen-Nürnberg

Fax: (+49) 913-185-28307

E-mail: dirk.guldi@chemie.uni-erlangen.de

[b] Departamento de Química Orgánica

Facultad de Ciencias Químicas

Universidad Complutense de Madrid

Ciudad Universitaria s/n

28040-Madrid (Spain)

E-mail: nazmar@quim.ucm.es

[c] Interdisciplinary Center for Molecular Materials

Friedrich-Alexander-Universität Erlangen-Nürnberg

Computer-Chemie-Centrum

Naegelsbachstrasse 25

91052, Erlangenand, Germany

[d] Instituto Madrileño de Estudios Avanzados en Nanociencia

(IMDEA. Nanociencia)

2

Experimental Section

Molecular Modelling: Calculations were performed using the program packages

Gaussian03 [35] and VAMP 10.0.[36] Molecular properties in the electronic ground

state were computed using density functional theory at the B3LYP/6-31G* (/6-311G**)

and the B3PW91/6-31G* (/6-311G**) levels and the restricted Hartree-Fock formalism

with the semi-empirical AM1* Hamiltonian.[S1] Excited-state calculations used a

singles-only configuration interaction (CIS) expansion with an active window of the

three to six highest occupied and lowest unoccupied molecular orbitals and the AM1

Hamiltonian.[S2] Test calculations with a singles only CI with up to 30 active orbitals

suggested that this level of theory is adequate for the problem. Excited-state geometries

were optimized in vacuo using numerical CI gradients.[S3] Solvent effects were

simulated in single-point calculations on the gas-phase optimized geometries using the

self-consistent reaction field solvation models with solvent-excluded surfaces with

atomic radii equal to 120% of those given by Bondi.[S4] Local electron affinity and

local ionization energy calculations [S5] on the AM1* optimized structures were

performed using Parasurf’07 A1 [S7] and visualized with Tramp 1.1d.[S7]

Compound 7: Compound 4 (1.14 g, 2.37 mmol) and p-ethynylbenzaldehyde 6 (324 mg,

2.48 mmol) were dissolved in dry piperidine (25 mL) and the system was flushed with

argon. Bis(triphenylphosphine)-palladium dichloride (106.75 mg, 0.152 mmol),

triphenylphosphine (30.95 mg, 0.118 mmol) and copper(I) iodine (22.56 mg, 0.118

mmol) was added. The mixture was stirred at room temperature for 16h.

Dichloromethane was added to the residue and washed with saturated NH4Cl, HCl

(10%) and NaCl. The organic phase was dried with MgSO4 and the solvent was

removed in vacuo. The crude product was purified by flash chromatography on silica

gel using hexane:AcOEt (9:1) as eluent to afford 7 (1.45 g, 2.61 mmol) as yellow solid.

Yield 41%. Mp 46-47 ºC. 1H- NMR (200 MHz, CDCl3, 25ºC): δ= 10.00 (s, 1H), 7.84

(d, J = 8.54 Hz, 2H), 7.64 (d, J = 8.05 Hz, 2H), 7.10 (s, 1), 7.00 (s, 1H), 4.00 (q, J =

1.95 Hz, 4H), 1.89-1.74 (m, 4H), 1.69-1.41 (m, 4H), 1.38-114 (m, 8H), 0.93-0.84 ppm

(m, 6H). 13C- NMR (75 MHz, CDCl3, 25ºC): δ= 191.27, 154.42, 149.49, 135.37,

131.93, 129.52, 117.93, 117.55, 114.35, 111.73, 93.06, 89.68, 70.14, 69.78, 31.54,

3

31.49, 29.21, 29.14, 25.70, 25.64, 22.61, 22.57, 14.00 ppm. FTIR (KBr): ν= 669, 756,

844, 1215, 1276, 1384, 1467, 1494, 1600, 1701, 2208, 2858, 2871, 2931, 2956, 3018,

3419 cm-1. MS (ESI): m/z (%): 486 (40) [M+], 402 (12), 316 (100). Anal. Calcd for

C27H33BrO3: %C: 66,80, %H: 6.85. Found: %C: 66,75, %H: 6.70.

2-Bromo-5-trimethylsilylacethynyl-1,4,bishexyloxybenzene 8 : 2-bromo-5-yodo-1,4-

dihexiloxibenzene 4 (1.23 g, 2.55 mmol) was dissolved in dry piperidine (25 mL)

Pd(PPh3)2Cl2 (44.22 mg, 0.063 mmol), PPh3 (33.31 mg, 0.12 mmol) and CuI (24 mg,

0.12 mmol) were added and stirred for 5 min, then trimethylsilylacetylene (4 mL, 2.81

mmol) was added to the solution. The mixture was stirred at room temperature for 3 h.

Dichloromethane was added to the mixture and washed with saturated NH4Cl, HCl

(10%) and NaCl. The organic phase was dried with MgSO4 and the solvent was

removed under vacuum. The crude product was purified by flash chromatography on

silica gel using hexane:AcOEt (9:1). The product was obtained as a white solid 8 (1.01

g, 2.22 mmol). Yield 87%. M.p.: 116 - 118 ºC. 1H-NMR (300 MHz, CDCl3, 25ºC): δ=

7.05 (s, 1H), 6.95 (s, 1H), 3.97-3.92 (m, 4H), 1.84-1.75 (m, 4H), 1.53-1.43 (m, 4H),

1.36-1.26 (m, 4H), 0.93-0.89 (m, 6H), 0.26 (s, 9H). 13C-NMR (75 MHz, CDCl3, 25ºC):

δ= 155.08, 149.65, 118.21, 113.94, 112.74, 101.03, 99.55, 70.40, 70.04, 32.01, 31.92,

30.13, 29.65, 29.54, 26.08, 26.05,23.05, 23.00, 14.49, 14.45 ppm. DEPT 135 (75 MHz,

CDCl3, 25ºC): δ= 118.21 (CH), 70.40 (CH2), 70.04 (CH2), 32.01 (CH2), 31.92 (CH2),

30.13 (CH2), 29.65 (CH2), 29.54 (CH2), 26.08 (CH2), 26.05 (CH2),23.05 (CH2), 23.00

(CH2), 14.49 (CH2), 14.45 ppm (CH3). FTIR (KBr), ν: 829, 856, 991, 1035, 1056, 1213,

1269, 1467, 1488, 1500, 2920, 2941, 2954 cm-1. EM m/z (EI), (%I): 454 (M+, 40), 368

(20), 286 (42), 271 (65), 43 (100).

Compound 9: Compound 8 (1.79 g, 3.94 mmol) and 6 (539 mg, 4.14 mmol) were

dissolved in dry toluene (30 mL) and the system was flushed with argon.

Tetrakis(triphenylphosphine)-palladium (228 mg, 0.197 mmol) and copper (I) iodine

(37.57 mg, 0.197 mmol) were added. The mixture was refluxed for 17 h. Ethyl acetate

was added to the residue and washed with saturated NH4Cl, HCl (10%) and NaCl. The

organic phase was dried with MgSO4 and the solvent was removed under vacuum. The

crude product was purified by flash chromatography on silica gel hexane: CH2Cl2 (20:1)

as eluent to afford 9 (510 mg, 1.034 mmol) as a yellow solid. Yield 65%. Mp 82-83 ºC. 1H- NMR (300 MHz, CDCl3, 25 ºC): δ= 10.02 (s, 1H), 7.86 (dd, J1 = 6.59 Hz, J2 = 1.65

4

Hz, 2H), 7.67 (brs, 2H), 3.99 (t, J = 6.1 Hz, 4H), 1.89-1.79 (m, 4H), 1.59-1.52 (m, 4H),

1.49-1.31 (m, 8H), 0.94-0.87 (m, 6H), 0.27 ppm (s, 9H). 13C- RMN (75 MHz, CDCl3):

δ= 191.78,154.52, 154.15, 135.75, 132.39, 130.18, 129.96, 117.55, 117.28, 115.03,

113.61, 101.33, 94.25, 90.55, 69.92, 32.01, 31.97, 29.69, 29.65, 26.13, 23.04, 14.48,

14.42, 0.33 ppm. FTIR (KBr): ν= 669, 756, 1215, 1465, 1488, 1600, 1701, 2399, 2931,

2958, 3018 cm-1. MS (ESI): m/z (%): 500 (100) [M+], 319 (84), 73 (24), 43 (47). Anal.

Calcd for C32H42O3Si: %C: 76.45, %H: 8.42. Found: %C: 76.56, %H: 8.61.

2-Triisopropylsilylethynyl-5-trimethylsilylethynyl-1,4-bishexyloxybenzene 11 :

Compound 8 (1.38 g, 3.04 mmol) was dissolved in dry toluene (25 mL), the system was

flushed with argon. Pd(PPh3)4 (106.75 mg, 0.152 mmol), CuI (29 mg, 0.152 mmol) and

diisisopropylamine (2mL) were added. The mixture was stirred for 5 min and then

triisopropylsilylacetylene (0.4 mL, 2.81 mmol) was added. The mixture was refluxed

for 24 h. Dichloromethane was added to the mixture and washed with saturated NH4Cl,

HCl (10%) and NaCl. The organic phase was dried with MgSO4 and the solvent was

removed under vacuum. The crude product was purified by flash chromatography on

silica gel using hexane:AcOEt (9:1). The product was obtained as a white solid 11 (1.45

g, 2.61 mmol). Yield 86%. M.p.: 115-116 ºC. 1H-NMR (300 MHz, CDCl3, 25ºC): δ=

6.88 (s, 2H), 3.98-3.91 (m, 4H), 1.79-1.77 (m, 4H), 1.57 (br, 3H), 1.52-1.47 (m, 4H),

1.36-1.30 (m, 8H), 1.14 (br, 18H), 0.93-0.90 (m, 6H), 0.25 ppm (s, 9H). 13C-NMR (75

MHz, CDCl3, 25ºC): δ= 155.08, 149.64, 118.21, 113.93, 112.72, 101.01, 99.57, 70.40,

70.04, 32.01, 31.92, 29.65, 29.53, 26.08, 26.05, 23.05, 23.01, 19.11, 14.50, 14.45,

11.76, 0.37 ppm. DEPT 135 (75 MHz, CDCl3): δ= 118.21 (CH), 70.40 (CH2), 70.04

(CH2), 32.01 (CH2), 31.92 (CH2), 29.65 (CH2), 29.53 (CH2), 26.08 (CH2), 26.05 (CH2),

23.05 (CH2), 23.01 (CH2), 19.11 (CH3), 14.50 (CH), 14.45 (CH), 11.76 (CH), 0.37 ppm

(CH3). FTIR (KBr): ν= 557, 613, 661, 810, 840, 862, 999, 031, 1058, 1201, 1222, 1247,

1272, 1384, 1404, 1467, 1498, 2150, 2866, 2895, 2941 cm-1. EM m/z (EI), (%I): 554

(M, 100), 427 (20), 343 (20), 73 (32), 43 (84).

2-Triisopropylsilylethynyl-5-ethynyl-1,4-bishexyloxybenzene 12 : Compound 11

(258 mg, 0.464 mmol) was dissolved in a mixture of THF:MeOH (1:1) 40 mL and

K2CO3 ( 64.49 mg, 0.464 mmol) was added to the solution. The solution was stirred at

room temperature for 2h. The mixture was extracted with dichloromethane and washed

with water (2 x 50mL). The organic phase was dried with MgSO4 and the solvent was

5

removed under vacuum. The product was purified by flash chromatography on silica gel

using hexane:CH2Cl2 (10:1) as eluent. The product was obtained as a yellow solid 12

(384.36 mg, 0.95 mmol). Yield 100%. M.p: 49-50 ºC. 1H-NMR (300 MHz, CDCl3,

25ºC): δ= 6.92 (brs, 2H), 3.94 (t, J = 6.5 Hz, 2H), 3.93 (t, J = 6.4 Hz, 2H), 3.33 (s, 1H),

1.85-1.72 (m, 4H), 1.48-1.38 (m, 4H), 1.36-1.28 (m, 8H), 1.26 (s, 21H), 0.93-0.89 ppm

(m, 6H). 13C-NMR (75 MHz, CDCl3, 25ºC): δ= 155.11, 149.73, 118.76, 118.35, 114.35,

111.68, 81.98, 79.92, 70.50, 70.21, 31.89, 29.51, 29.45, 26.03, 25.95, 22.97, 19.09,

14.41, 11.76 ppm. DEPT 135 (75 MHz, CDCl3): δ= 118.76 (CH), 118.35 (CH), 81.98

(CH), 70.50 (CH2), 70.21 (CH2), 31.89 (CH2), 29.51 (CH2), 29.45 (CH2), 26.03 (CH2),

25.95 (CH2), 22.97 (CH2), 19.09 (CH3), 14.41(CH3), 11.76 ppm (CH3). FTIR (KBr): ν=

659, 713, 729, 769, 810, 999, 1031, 1056, 1199, 1220, 1272, 1467, 1498, 1541, 2152,

2864, 2895, 2923, 2943, 3421 cm-1. EM m/z (EI), (%I): 482 (M, 7), 382 (20), 298 (12),

214 (100), 55 (19).

Compound 13: Compound 5 (97.89 g, 0.421 mmol) and compound 12 (224.04 mg,

0.464 mmol) were dissolved in dry THF (25 mL) and the system was flushed with

argon. Tetrakis(triphenylphosphine)-palladium (24.26 mg, 0.02 mmol), copper (I)

iodine (4 mg, 0.02 mmol) and diisopropylamine ( 1mL) were added. The mixture was

refluxed for 24h. Ethyl acetate was added to the residue and washed with saturated

NH4Cl, HCl (10%) and NaCl. The organic phase was dried with MgSO4 and the solvent

was removed under vacuum. The crude product was purified by flash chromatography

on silica gel using hexane:CH2Cl2 (20:1) as eluent to afford 13 (164.33 mg, 0.28 mmol)

as a yellow solid. Yield 67%. 1H-NMR (300 MHz, CDCl3, 25º): δ= 10.01 (s, 1H), 7.84

(dd, J1 = 6.59 Hz, J2 = 1.65 Hz, 2H), 7.58 (dd, J1 = 6.59 Hz, J2 = 1.65 Hz, 2H), 6.95

(brs, 2H), 4.01 (t, J = 6.2 Hz, 4H), 1.89-1.79 (m, 4H), 1.59-1.52 (m, 4H), 1.49-1.31 (m,

8H), 1.00 (brs, 3H), 0.8 (s, 18H), 0.4-0.6 ppm (m, 6H). 13C-NMR (75 MHz, CDCl3, 25

ºC): δ= 191.30, 158.43, 157.81, 135.80, 132.18, 129.60, 125.0, 119.89, 119.27, 118.22,

109.30,107.23, 86.12, 88.0, 68.46, 31.54, 29.53, 25.65, 22.5, 18.67, 13.97, 11.38 ppm.

FTIR (KBr): ν= 669, 756, 1215, 1465, 1488, 1600, 1701, 2399, 2931, 2958, 3018 cm-1.

MS (ESI): m/z (%): 585 (100) [M+], 444 (80), 73 (45), 43 (60). Anal. Calcd for

C38H54O3Si: %C 77.76, %H 9.27. Found: %C: 77.56, %H: 8.91.

Compound 14: Compound 9 (884.2 mg, 1.75 mmol) was dissolved in a mixture of

THF:MeOH (1:1) 40 mL and K2CO3 ( 242.91 mg, 1.75 mmol) was added to the

6

solution. The solution was stirred at room temperature for 12h. The mixture was

extracted with dichloromethane and washed with water. The organic phase was dried

with MgSO4. The solvent was removed and the product was purified by flash

chromatography on silica gel using hexane:AcOEt (15:1) as eluent. The product was

obtained as a yellow solid 14 (686 mg, 1.42 mmol). Yield 81 %. Mp. 70-71 ºC. 1H-

NMR (300 MHz, CDCl3, 25ºC): δ= 9.95 (s, 1H), 7.81 (dd, J1 = 6.61 Hz, J2 = 1.79 Hz,

2H), 7.61-7.57 (d, 2H), 6.93 (brs, 2H), 3.97-3.90 (m, 4H), 1.80-1.68 (m, 4H), 1.49-1.18

(m, 12H), 0.86-0.78 ppm (m, 3H). 13C-NMR (75 MHz, CDCl3, 25 ºC): δ= 191.85,

154.48, 154.08, 135.77, 132.44, 130.10, 129.99, 117.98, 117.22, 113.98, 113.83, 94.30,

90.31, 80.23, 70.05, 69.92, 31.98, 31.93, 30.12, 29.64, 29.50, 26.14, 26.0, 23.05, 23.0,

14.45 ppm. MS (ESI): m/z (%): 430 (M, 80), 429 (M+, 70), 230 (55), 206 (45). Anal.

Calcld for C29H34O3: %C 80.89, %H 7.96. Found: %C: 80.56, %H: 8.01.

Compound 15: Compound 14 (142.42 mg, 0.325 mmol) and compound 4 (140 mg,

0.325 mmol) were dissolved in dry piperidine (15 mL) and the system was flushed with

argon. Bis(triphenylphosphine)-palladium dichloride (6 mg, 8.12x10-3 mmol),

triphenylphosphine (4.26 mg, 0.016mmol) and copper(I) iodine (3 mg, 0.016 mmol)

were added. The mixture was stirred at room temperature for 3h. Dichloromethane was

added to the mixture and washed with saturated NH4Cl, HCl (10%) and NaCl. The

organic phase was dried with MgSO4 and the solvent was removed under vacuum. The

crude product was purified by flash chromatography on silica gel using hexane: CH2Cl2

(20:1) as eluent. The product was obtained as a yellow solid 15 (210 mg, 0.118 mmol).

Yield 14%. M.p.: 87-89 ºC. 1H- NMR (200 MHz, CDCl3, 25ºC): δ= 10.02 (s, 1H), 7.87

(d, J = 8.3 Hz, 2H), 7.66 (d, J = 7.92 Hz, 2H), 7.09 (brs, 1H),7.00 (brs, 2H), 6.98 (s,

1H), 4.1-3.97 (m, 8H), 1.83-1.76 (m, 8H), 1.6-1.34 (m, 8H),1.34-1.25 (m, 16H), 1.00-

0.88 ppm (m,12H). 13C- NMR (75 MHz, CDCl3, 25ºC): δ= 191.43, 155.00, 154.91,

154.08, 153.72, 153.29, 149.46, 135.40, 132.03, 129.56, 118.18, 117.75, 117.56,

116.96, 115.45, 113.52, 112.75, 77.23, 76.73, 76.28, 74.94, 73.91, 73.12, 69.94, 69,83,

69.75, 69.54, 31.54, 31.51, 29.67, 29.18, 29.14, 29.09, 25.63, 25.59, 22.60, 22.57,

18.67, 18.64, 17.76, 16.22, 16.02, 15.74, 13.98 ppm. FTIR (KBr): ν= 650, 745, 770,

800, 1126, 1310, 1645, 2255 cm -1. EM m/z (ESI), (%I): 783 (M+, 70),705 (55),

604(45), 579 (35).

7

Compound 16: Compound 8 (70.22 mg, 0.154 mmol) and compound 14 (70 mg, 0.162

mmol) were dissolved in dry THF (15 mL) and the system was flushed with argon.

Tetrakistriphenylphosphine palladium (8.89 mg, 7.7x10-3 mmol), copper(I) iodine (1.46

mg, 7.7x10-3 mmol) and diisopropylamine (1mL) were added. The mixture was heated

for 28 h. Dichloromethane was added to the mixture and washed with saturated NH4Cl,

HCl (10%) and NaCl. The organic phase was dried with MgSO4 and the solvent was

removed under vacuum. The crude product was purified by flash chromatography on

silica gel using hexane: AcOEt (9:1) as eluent. The product was obtained as a yellow

solid 16 (20 mg, 0.002 mmol). Yield 17%. M.p: 77-79 ºC. 1H-NMR (300 MHz, CDCl3,

25ºC): δ= 10.03 (s, 1H), 7.88 (d, J = 8.23 Hz, 2H), 7.67 (d, J = 8.24 Hz, 2H), 7.02 (brs,

2H), 6.97 (br, 2H), 4.05 (t, J = 6.5 Hz, 8H), 1.90-1.77 (m, 8H), 1.57-1.53 (m, 8H), 1.37-

1.26 (m, 16H), 0.95-0.85 (m, 12H), 0.27 ppm (s, 9H). 13C-NMR (75 MHz, CDCl3,

25ºC): δ= 191.86, 154.53, 154.27, 153.82, 153.75, 135.71, 132.40, 129.99, 117.70,

117.41, 117.37, 117.31, 115.57, 114.69, 114.19, 113.31, 101.52, 100.63, 94.31, 92.29,

91.69, 90.71, 70.11, 70.0, 69.87, 69.82, 32.01, 29.69, 29.65, 26.16, 26.12, 26.97, 23.05,

14.45, 0.36 ppm. DEPT 135 (75 MHz, CDCl3, 25ºC) : δ= 191.86 (CHO), 132.40 (CH),

129.99 (CH), 117.70 (CH), 117.41 (CH), 117.37 (CH), 117.31 (CH), 70.11 (CH2), 70.0

(CH2), 69.87 (CH2), 69.82 (CH2), 32.01 (CH2), 29.69 (CH2), 29.65 (CH2), 26.16 (CH2),

26.12 (CH2), 26.97 (CH2), 23.05 (CH2), 14.45 (CH2), 0.36 ppm (CH3). FTIR (KBr): ν=

669, 756, 1215, 1465, 1488, 1600, 1701, 2399, 2931, 2958, 3018 cm-1. EM m/z (ESI),

(%I): 802 (M+, 70), 619 (80), 413 (30).

Compound 17: 1H-NMR (300 MHz, CDCl3, 25ºC): δ= 10.03 (s, 2H), 7.87 (d, J = 8.5

Hz, 4H), 7.66 (d, J = 8.3 Hz, 4H), 7.01 (s, 4H), 4.03 (t, J = 6.4 Hz, 8H), 1.90-1.81 (m,

8H), 1.54-1.52 (m, 8H), 1.38-1.26 (m, 24H), 0.95-0.88 ppm (m, 12H). 13C-NMR (75

MHz, CDCl3, 25ºC): δ= 191.85, 155.32, 154.10, 135.81, 132.46, 130.00, 117.88,

117.26, 114.51, 113.73, 94.89, 90.39, 80.01, 79.96, 70.18, 69.90, 31.98, 31.94, 29.62,

29.48, 26.14, 26.01, 23.06, 23.02, 14.47 ppm. FTIR (KBr): ν= 729, 775, 823, 997,

1028, 1163, 1213, 1217, 1388, 1411, 1467, 1492, 1600, 1701, 2206.4, 2345, 2729,

2852, 2923 cm-1. EM m/z (ESI), (%I): 881 (M + Na, 10), 857 (M+, 40), 785 (30).

Compound 18: Compound 8 (357 mg, 0.788 mmol) and 12 (400 mg, 0.828 mmol)

were dissolved in dry THF (50 mL) and the system was flushed with argon. Pd(PPh3)4

(45.52 mg, 0.039 mmol), CuI (7.5 mg, 0.039 mmol) and iPr2NH ( 0.3mL) were added.

8

The mixture was heating under reflux for 48 h. Dichloromethane was added to the

mixture and washed with saturated NH4Cl, HCl (10%) and NaCl. The organic phase

was dried with MgSO4 and the solvent was removed. The crude product was purified by

flash chromatography on silica gel using hexane: AcOEt (9:1) as eluent. The product

was obtained as yellow solid 17 (683.39 mg, 0.709 mmol). Yield 90%. M.p.: 62-64 ºC. 1H- NMR (300 MHz, CDCl3, 25ºC): δ= 6.92 (s, 2H), 6.91 (s, 2H), 3.99 (t, J = 6.5 Hz,

4H), 3.93 (t, J= 6.3 Hz, 4H), 1.82-1.79 (m, 8H), 1.50-1.48 (m, 8H), 1.38-1.26 (m, 16H),

0.94-0.89 ppm (m, 12H). 13C-NMR (75 MHz, CDCl3, 25ºC): δ= 155.12, 154.53, 118.04,

117.48, 115.44, 112.97, 104, 97.8, 80, 79.9, 70.25, 69.64, 32.07, 31.94, 30.11, 29.76,

29.52, 26.24, 26.00, 23.04, 23.00, 19.10, 14.49, 14.45, 11.76 ppm. EM m/z (ESI), (%I):

963 (M, 40), 95 (M+, 60), 963 (20), 877 (10). FTIR (KBr), ν: 659, 862, 945, 997, 1047,

1072, 1197, 1220, 1271, 1384, 1400, 2854, 2925, 2954 cm-1.

Compound 19: Compound 4 (632.35 mg, 1.443 mmol) and 12 (697 mg, 1.443 mmol)

were dissolved in dry piperidine (15 mL) and the system was flushed with argon.

Bis(triphenylphosphine)-palladium dichloride (25.32 mg, 0.036 mmol),

triphenylphosphine (18.88 mg, 0.072 mmol) and copper(I) iodine (13.74 mg, 0.072

mmol) were added. The mixture was stirred at room temperature for 3h.

Dichloromethane was added to the mixture and washed with saturated NH4Cl, HCl

(10%) and NaCl. The organic phase was dried with MgSO4 and the solvent was

removed under vacuum. The crude product was purified by flash chromatography on

silica gel using hexane: CH2Cl2 (10:1) as eluent. The product was obtained as a yellow

solid 19 (665 mg, 0.793 mmol). Yield 55%. M.p.: 58-60ºC. 1H-NMR (200 MHz,

CDCl3, 25ºC): δ= 7.08 (s, 1H), 7.00 (s, 1H), 6.93 (s, 2H), 4.04-3.88 (m, 8H), 189-1.70

(m, 8H), 1.55-1.46 (m, 8H), 1.37-1.25 (m, 16H), 1.14 (brs, 21H), 0.93-0.87 ppm (m,

12H). 13C-NMR (75 MHz, CDCl3, 25ºC): δ= 154.34, 154.04, 153.23, 149.46, 118.19,

117.95, 117.77, 116.55, 114.29, 114.04, 113.25, 112.99, 103.00, 96.47, 90.64, 90.61,

70.09, 69.96, 69.82, 69.27, 31.67, 31.60, 31.56, 31.50, 29.69, 29.43, 29.30, 29.20,

29.17, 25.84, 25.64, 25.60, 22.57, 18.69, 14.04, 14.00, 11.38 ppm. EM m/z (ESI), (%I):

863 (M++Na, 70), 837 (M+, 20), 686 (30). 403 (30), 203 (45). FTIR (KBr), ν: 756, 908,

1647, 2252, 2399 cm-1.

Compound 20: Compound 19 (308 mg, 0.368 mmol) and trimethylsilylacetylene

(0.16mL, 1.189 mmol) were dissolved in dry THF (15 mL) and the system was flushed

9

with argon. Pd(PPh3)4 (45.06 mg, 0.039 mmol), copper(I) iodine (7.55 mg, 0.039 mmol)

and diisopropylamine (0.33mL) were added. The mixture was stirred and heating at

reflux during for 4 days. Dichloromethane was added to the mixture and washed with

saturated NH4Cl, HCl (10%) and NaCl. The organic phase was dried with MgSO4 and

the solvent was removed under vacuum. The crude product was purified by flash

chromatography on silica gel using hexane: CHCl3 (90:1) as eluent. The product was

obtained as a yellow solid 20 (306.3 g, 0.358 mmol). Yield 97%. M.p: 70-72 ºC. 1H-

NMR (300 MHz, CDCl3, 25ºC): δ= 6.94 (brs, 4H), 3.99-3.93 (m, 8H), 1.85-1.79 (m,

8H), 1.6-1.4 (m, 8H), 1.39-1.30 (m, 24H), 1.2-1.05 (m, 21H), 0.90-0.87 (m, 12H), 0.26

ppm (s, 9H). 13C-NMR (75 MHz, CDCl3, 25ºC): δ= 154.35, 154.20, 153.36, 153.28,

117.93, 117.43, 117.05, 116.59, 114.61, 114.34, 114.05, 113.67, 103.05, 101.23,

100.08, 96.53, 91.61, 91.22, 69.86, 69.68, 69.47, 69.27, 31.72, 31.65, 30.95, 29.74,

29.47, 29.34, 29.29, 25.89, 25.74, 25.68, 22.66, 18.74, 14.10, 14.06, 11.42, 0.00 ppm.

EM m/z (ESI), (%I): 854 (M, 40), 756. FTIR (KBr): ν= 636, 769 , 812, 1029, 1211,

1274, 1340, 1386, 1419, 1458, 1473, 2148, 2864, 2941 cm-1.

Compound 21: Compound 20 (306.3 g, 0.358 mmol) was dissolved in a mixture of

THF:MeOH (1:1) 40 mL and K2CO3 (49.76 mg, 0.358 mmol) was added to the

solution. The solution was stirred at room temperature for 2h. The mixture was

extracted with dichloromethane and washed with water. The organic phase was dried

with MgSO4 and the solvent was removed under pressure. The product was purified by

flash chromatography on silica gel using hexane:AcOEt (15:1) as eluent. The product

was obtained as a yellow solid 21 (280.40 mg, 0.358 mmol). Yield 100 %. 1H-NMR

(300 MHz, CDCl3, 25ºC): δ= 7.04 (s, 1H), 7.01 (s, 1H), 6.99 (s, 1H), 6.97 (s, 1H), 4.08-

3.93 (m, 8H), 3.35 (s, 1H), 2.05.1.79 (m, 8H), 1.51-1.44 (m, 8H), 1.34-1.32 (m, 24H),

1.26 (brs, 3H) 1.15 (s, 18H), 0.91-0.84 ppm (m, 12H). 13C-NMR (75 MHz, CDCl3,

25ºC): δ= 154.71, 154.53, 153.68, 153.66, 118.27, 117.39, 116.91, 115.35, 114.58,

114.47, 112.87, 103.38, 96.96, 92.03, 91.37, 82.67, 80.45, 78.65, 70.19, 70.09, 69.98,

69.63, 37.50, 32.10, 32.01, 31.94, 30.11, 29.84, 29.70, 29.63, 29.54, 26.27, 26.05,

26.01, 23.04, 22.99, 19.11, 14.53, 14.49, 14.44, 11.78 ppm. FTIR (KBr): ν= 735, 845,

900, 1140, 1250, 1270, 1315, 1625, 2230, 3250 cm-1. EM m/z (ESI), (%I): 781 (M+, 55),

782 (M, 15), 560 (47).

10

Compound 22: Compound 21 (70.22 mg, 0.154 mmol) and 5 (70 mg, 0.162 mmol)

were dissolved in dry THF (15 mL) and the system was flushed with argon. Pd(PPh3)4

(8.89 mg, 7.7 x 10-3 mmol), copper(I) iodine (1.46 mg, 7.7 x 10-3 mmol) and

diisopropylamine (1 mL) were added. The mixture was refluxed for 28 h.

Dichloromethane was added to the mixture and washed with saturated NH4Cl, HCl

(10%) and NaCl. The organic phase was dried with MgSO4 and the solvent was

removed under vacuum and the crude product was purified by flash chromatography on

silica gel using hexane: AcOEt (9:1) as eluent. The product was obtained as a yellow

solid 22 (20 mg, 0.002 mmol). Yield 64%. M.p: 77-78 ºC. 1H-NMR (300 MHz, CDCl3,

25ºC): δ= 10.00 (s, 1H), 7.84 (d, J = 8.2 Hz, 2H), 7.56 (d, J = 8.2 Hz, 2H), 6.95 (brs,

4H), 3.7-3.8 (m, 8H), 1.8-1.6 (m, 8H), 1.51-1.24 (m, 8H), 0.9 (brs, 3H), 0.6 (brs, 21H),

0.6-0.4 ppm (m, 12H). 13C-NMR (75 MHz, CDCl3, 25ºC): δ= 191.83, 156.76, 155.80,

154.80, 149.87, 135.75, 132.37, 130.17, 129.98, 119.89, 118.30, 117.92, 114.73,

112.07, 109.30, 107.23, 105.53, 93.46, 90.06, 70.55, 70.18, 32.33, 31.95, 31.91, 30.10,

29.77, 29.60, 29.53, 26.10, 26.05, 23.10, 23.10, 23.03, 22.9, 18.67, 14.53, 14.43, 11.38

ppm. FTIR (KBr): ν= 770, 865, 1218, 1282, 1465, 1697, 2260, 2320, 2570 cm-1. EM

m/z (ESI), (%I): 885 (M+, 55), 872 (67), 746 (100), 692 (32), 606 (84), 292 (33).

2-Trimethylsilylethynyl-5-iodo-1,4-bishexyloxybenzene 23: Compound 8 (1g, 2.204

mmol) was dissolved in dry THF (20mL), n-BuLi (2.204 mmol) was slowly added at 0

ºC. The mixture was stirring for 3 h at 0 ºC. After, I2 (559 mg, 2.204 mmol) solution in

dry THF (10 mL) was added and stirring for 12 h at room temperature. The mixture was

washed with Na2S2O3, NaCl and the organic phase was dried with MgSO4. The solvent

was removed under pressure and the crude product was purified by flash

chromatography on silica gel using hexane as eluent. The product was obtained as white

solid 23 (1.763 mmol). Yield 80%. 1H-NMR (300 MHz, CDCl3, 25ºC): δ= 7.25 (s, 1H),

6.83 (s, 1H), 3.96-3.93 (m, 4H), 1.82-1.72 (m, 4H), 1.53-1.42 (m, 4H), 1.36-1.25 (m,

4H), 0.94-0.88 (m, 6H), 0.25 ppm (s, 9H). 13C-NMR (75 MHz, CDCl3, 25ºC):

δ= 155.25, 155.06, 124.15, 116.67, 113.76, 101.17, 99.82, 88.30, 70.46 70.14, 32.00,

31.89, 30.11, 29.67, 29.53, 26.14, 26.07, 23.04, 23.00, 14.48, 14.45, 0.34 ppm. FTIR

(KBr): ν= 761, 808, 1205, 1375, 1460, 2153 cm-1. EM m/z (EI), (%I): 500 (M, 100),

442 (67), 330 (55).

11

Compound 24: Compound 16 (150 mg, 0.186 mmol) was dissolved in a mixture of

THF:MeOH (1:1) (40 mL) and K2CO3 ( 25.85 mg, 0.186 mmol) was added to the

solution. The solution was stirred at room temperature for 2 h. The mixture was

extracted with dichloromethane and washed with water (2 x 50 mL). The organic phase

was dried with MgSO4. The solvent was removed under vacuum and the product was

purified by flash chromatography on silica gel hexane:AcOEt (15:1) as eluent to afford

24 as yellow solid. Yield 100%.

Compound 22 (150 mg, 0.186 mmol) was dissolved in THF (40 mL) and

tetrabutylammonium fluoride (0.186 mmol) was added to the solution. The solution was

stirred at room temperature for 1 h. The mixture was extracted with dichloromethane

and washed with water (2 x 50 mL). The organic phase was dried with MgSO4. The

solvent was removed under vacuum and the product was purified by flash

chromatography on silica gel using hexane:AcOEt (15:1) as eluent to afford 24 as

yellow solid. Yield 90 %.1H-NMR (300 MHz, CDCl3, 25ºC): δ= 10.02 (s, 1H), 7.87 (d,

J = 8.07 Hz, 2H), 7.64 (d, J=8.04 Hz, 2H), 7.10-6.93 (m, 4H), 4.22 (t, J = 5.4 Hz, 8H),

3.36 (s, 1H), 1.88-1.83 (m, 8H), 1.68-1.51 (m, 8H), 1.34-1.25 (m, 16H), 0.91-0.89 ppm

(m, 12H). 13C-NMR (75 MHz, CDCl3, 25ºC): δ= 191.83, 154.52, 154.28,153.85,153.72,

135.72, 132.39, 130.21, 129.99, 118.23, 117.39, 117.31, 115.47, 115.11, 113.40,

113.10, 94.35, 92.35, 91.75, 90.69, 82.84, 80.41, 70.09, 69.97, 69.87, 32.01, 31.94,

30.12, 29.70, 29.65, 29.54 , 26.17, 26.06, 23.06, 23.O, 14.46 ppm. FTIR (KBr): ν= 733,

856, 950, 1130, 1210, 1470, 1578, 1645, 2230 cm-1. EM m/z (ESI), (%I): 840 (M+, 70),

619 (80), 413 (30).

General procedure for the preparation of exTTF-oPPE dyad 26a-b : Dyad 26a: 4-

Ethynylbenzaldehyde 6 (30.84 mg, 0.237 mmol) and compound 25 (80 mg, 0.158

mmol) was dissolved in dry piperidine (10 mL) then the system was flushed with argon.

Bis(triphenylphosphine)-palladium dichloride (2.8 mg, 0.004 mmol),

triphenylphosphine (1.16 mg, 0.004mmol) and copper (I) iodine (1 mg, 0.004 mmol)

were added. The mixture was stirred at room temperature for 24 h. Dichloromethane

was added to the residue and washed with saturated NH4Cl, water and NaCl. The

organic phase was dried with MgSO4 and the solvent was removed under vacuum. The

crude product was purified by flash chromatography on silica gel using hexane:CH2Cl2

(3:1) to afford 26a as red solid (210 mg, 0.118 mmol). Yield 85% . Mp. 183-184 ºC. 1H-

12

NMR (CDCl3, 300 MHz, 25 ºC): δ= 10.01 (s, 1H), 7.88 (brs, 1H), 7.87-7.84 (m, 2H),

7.72-7.66 (m, 5H), 7.32-7.26 (m, 2H), 6.30 ppm (s, 4H). 13C-NMR (CDCl3, 75 MHz,

25ºC): δ= 191.39, 137.27, 136.86, 136.04, 135.3, 135.34, 135.15, 135.14, 132.12,

129.73, 129.56, 129.31, 128.06, 126.14, 125.07, 124.98, 124.91, 121.53, 121.07,

119.69, 117.38, 117.32, 117.28, 117.12, 93.96, 88.79 ppm. FTIR(KBr): ν= 640, 669,

754, 1163, 1259, 1458, 1508, 1546, 1600, 1607, 1697, 2923 cm-1. UV/vis (CH2Cl2):

λmax: 230, 332, 363, 387, 445 nm. MS (ESI): m/z (%): 508 (100) [M+], 406 (12), 254

(12). Anal. Cacld for C29H16OS4: %C: 68.47, %H: 3.17. Found: %C: 69.53, %H: 4.43.

Dyads 26b-c: Compound 25 (111.92 mg, 0.221 mmol) and compound 14 (100 mg,

0.232 mmol) were dissolved in dry THF (30 mL) and the system was flushed with

argon. Tetrakis(triphenylphosphine)-palladium (6.4 mg, 5.53x10-3 mmol), copper (I)

iodine (84.9 mg, 6.18853x10-3 mmol) and diisopropylamine (1mL) were added to the

solution. The mixture was refluxed for 3h (26b) and 48 h (26c). The mixture was

extracted with dichloromethane and washed with NH4Cl, water and NaCl. The organic

phase was dried with MgSO4 and the solvent was removed under vacuum. The solid

was purified by flash chromatography on silica gel.

Dyad 26b: Eluent: hexane:CH2Cl2 (3:1). 26b was obtained as red solid 115 (94.3 g,

0.11 mmol). Yield 50 %. Mp. 207-208 ºC. 1H-NMR (300 MHz, CDCl3, 25 ºC): δ=

10.03 (s, 1H), 8.46 (d, J = 1.51 Hz, 1H), 8.36-8.30 (m, 3H), 7.92-7.82 (m, 4H), 7.77-

7.68 (m, 3H), 7.08 (s, 1H), 7.06 (s, 1H), 6.95 (brs, 4H), 4.09-4.03 (m, 4H), 1.91-1.85

(m, 4H), 1.6-1.55 (m, 4H), 1.39-1.26 (m, 8H), 0.93-0.89 ppm (m, 6H). 13C-NMR (75

MHz, CDCl3, 25 ºC): δ= 191.86, 182.92, 154.30, 154.23, 136.83, 135.81, 134.75,

134.63, 133.97, 133.82, 132.74, 132.71, 132.60, 132.47, 131.98, 131.94, 130.57,

130.01, 129.0, 128.84, 127.80, 127.73, 117.75, 117.56, 117.26, 117.18 (CH), 114.48,

114.02, 76.43, 76.02, 75.63, 70.04, 69.98, 31.99, 30.11, 29.66, 26.17, 23.07, 14.47 ppm.

FTIR (KBr): ν= 669, 756, 1215, 1467, 1488, 1508, 1600, 1701, 2343, 2360, 2931, 2958,

3018 cm-1. MS (ESI): m/z (%): 809 (15) [M+], 808 (M+, 88), 707 (75), 637 (10).

UV/vis (CH2Cl2) : λmax: 446, 402, 317, 228 nm. Anal. Calcd for C49H44O3S4: %C:

72.74, %H: 5.48. Found: %C: 72.80, % H: 5.40.

Dyad 26c: Eluent:hexane: CH2Cl2 (1:1). 26c was obtained as a yellow solid (94.3 g,

0.11 mmol) with 38% yield. Mp: 135-135 ºC. 1H-NMR (300 MHz, CDCl3, 25ºC): δ=

13

10.03 (s, 1H), 7.89 (brs, 2H), 7.73-7.67 (m, 5H), 7.45 (dd, J1 = 8.09 Hz, J2 = 1.51 Hz,

1H), 7.33-7.30 (m, 2H), 7.04 (brs, 4H), 6.33 ppm (d, J = 4.5 Hz, 4H). 13C-NMR (75

MHz, CDCl3, 25ºC): δ= 191.84, 154.31, 154.11, 153.97, 153.85, 144.63, 137.04,

136.93, 135.90, 135.71, 135.61, 132.40, 130.27, 129.99, 129.48, 128.27, 126.48,

125.39, 125.31, 122.17, 121.72, 121.19, 117.70, 117.57, 117.48, 117.35, 115.70,

114.76, 114.34, 113.28, 95.86, 94.29, 92.50, 91.67, 90.75, 86.67, 70.16, 70.08, 69.90,

32.33, 32.12, 32.04, 32.01, 30.76, 30.11, 29.84, 29.70, 26.27, 26.17, 26.09, 23.39,

23.10, 23.06, 14.55, 14.47 ppm. FTIR (KBr): ν= 756, 908, 1647, 2252, 2399 cm-1. EM

m/z (ESI), (%I): 1108 (M+, 70), 1008 (80), 777 (30). 685 (30). UV-vis (CH2Cl2), λmax:

233, 277, 309, 366, 412 nm. Anal. Calcd for C69H72O5S4: %C 74.69, %H 6.54. Found:

%C: 74.55, %H: 6.60.

General procedure for the preparation of exTTF-oPPE-C60 triads 27a-c:

[60]fullerene (85 mg, 0.118 mmoles) was dissolved in chlorobenzene (ultrasound 30

min), the corresponding aldehyde N-methylglycine (1.5eqv) was added. The mixture

was heated under reflux for 3 h. After the evaporation of the solvent, the residue was

purified by flash chromatography on silica gel. The black solid obtained after

chromatography was further purified by repeated centrifugation in methanol and diethyl

ether to yield the corresponding triads 27a-c as brown solids.

Compound 27a: Eluent: CS2:hexano (2:1). Yield 33%. Mp > 300 ºC.1H- NMR (300

MHz,CDCl3, 25ºC): δ= 7.87 (brs, 2H), 7.76 (brs, 1H), 7.69-7.63 (m, 5H), 7.42-7.29 (m,

3H), 6.38 (d, J = 6.8 Hz, 4H), 5.09 (s, 1H), 5.05 (s, 1H), 4.38 (d, J=9.33 Hz, 1H), 2.94

ppm (s, 3H). 13C- NMR (75 MHz, CDCl3, 25ºC): δ= 156.53, 154.28, 153.63, 153.38,

147.84, 147.81, 147.15, 146.93, 146.89, 146.82, 146.78, 146.74, 146.70, 146.65,

146.57, 146.50, 146.29, 146.19 146.17, 146.02, 145.96, 145.91, 145.86, 145.79, 145.73,

145.25, 144.94, 143.72, 143.60, 143.26, 143.19, 143.16, 142.86, 142.80, 142.71,

142.67, 142.61, 142.48, 142.46, 142.25, 142.16, 140.82, 140.78, 140.61, 140.24,

138.07, 138.04, 137.57, 137.47, 137.15, 136.48, 136.32, 136.05, 135.89, 135.69,

132.67, 130.28, 129.90, 129.80, 129.27, 128.41, 126.89, 126.86, 125.62, 125.58,

125.51, 124.52, 122.26, 121.78, 121.29, 118.94, 118.12, 118.02, 92.15, 90.88, 83.81,

77.65, 70.62, 69.47, 40.67, 30.86 ppm. FTIR(KBr): ν= 527, 1259, 1375, 1460, 2923,

2850, 3434 cm-1. UV-vis (CH2Cl2) : λmax: 232, 255, 313, 376, 431, 444 nm. EM m/z

(EI), (%I): 1255 (100) [M], 1254 [M+].

14

Compound 27b: Eluent: toluene. Yield 63%. Mp > 300 ºC. 1H-NMR (300 MHz,

CDCl3, 25ºC): δ= 8.4 (d, J = 1.5 Hz, 1H), 8.35-8.29 (m, 3H), 7.90 (dd, J1 = 8.1 Hz, J2 =

1.65, 2H), 7.87-7.81 (m, 3H), 7.64-7.61 (d, J = 7.96, 2H), 7.05 (s, 1H), 7.03 (s, 1H),

6.79 (s, 4H), 5.03 (d, J =9.19 Hz, 1H), 4.98 (s, 1H), 4.30 (d, J = 9.19 Hz, 1H), 4.07-4.02

(m, 4H), 2.86 (s, 3H), 1.90-1.83 (m, 4H), 1.6-1.5 (m, 4H), 1.38-1.35 (m, 8H), 0.92-0.87

ppm (m, 6H). 13C-NMR (75 MHz, CDCl3, 25ºC): δ= 193.17, 183.01, 182.90, 155.68,

154.35, 154.04, 147.77, 146.76, 146.66, 146.36, 145.70, 145.13, 144.75, 143.56,

143.04, 142.51, 142.38, 142.08, 140.59, 140.32, 140.04, 136.79, 134.57, 133.99,

133.90, 132.65, 132.51, 130.52, 129.88, 127.76, 127.71, 118.75, 117.38, 117.20,

114.47, 113.35, 93.89, 91.54, 75.88, 70.02, 40.46, 39.88, 35.11, 31.95, 30.12, 29.63,

26.15, 23.04, 14.48, 14.43 ppm. FTIR (KBr): ν= 527, 669, 758, 1186, 1217, 1222,

2395, 2150, 2175 cm-1. EM m/z (EI), (%I): 1554 (56)[ M+], 1384 (35). UV-vis

(CH2Cl2), λmax: 250, 317, 384, 491 nm.

Compound 27c : Eluent : chloroform. Yield 53 %. Mp > 300 ºC. 1H-NMR (300 MHz,

CDCl3, 25ºC): δ= 8.45 (brs, 1H), 8.36-8.30 (m, 3H), 7.91-7.82 (m, 5H), 7.63-7.60 (m,

2H), 7.06 (s, 2H), 7.04 (s, 2H), 7.01 (s, 2H), 7.00 (s, 2H), 5.02 (d, J = 9.19 Hz, 1H),

4.99 (s, 1H), 4.30 (d, J = 9.19 Hz, 1H), 4.09-4.01 (m, 4H), 2.85 (s, 3H), 1.88-1.80 (m,

4H), 1.59-1.57 (m, 4H), 1.36-1.26 (m, 8H), 0.93-0.84 ppm (m, 6H). 13C-NMR (75 MHz,

CDCl3, 25ºC): δ= 183.03, 182.92, 154.35, 154.10, 153.90, 153.86, 147.81, 146.80,

146.67, 146.43, 146.37, 146.26, 146.12, 145.93, 145.79, 145.72, 145.16, 144.93,

144.67, 143.56, 143.41, 143.12, 142.83, 142.54, 142.48, 142.29, 142.06, 141.90,

140.65, 140.58, 140.36, 140.13, 136.79, 135.84, 134.71, 134.60, 133.99, 133.89,

133.83, 132.88, 132.84, 132.74, 132.62, 132.44, 131.93, 131.30, 130.52, 130.25,

129.85, 129.74, 129.20, 128.99, 128.81, 128.68, 127.78, 127.71, 11751, 117.38, 115.76,

114.90, 113.88, 113.15, 93.87, 92.40, 91.95, 91.67, 83.64, 70.12, 70.09, 69.95, 68.55,

32.02, 31.97, 31.95, 30.11, 29.66, 26.07, 23.06, 14.49, 14.46 ppm. FTIR (KBr): ν= 526,

756, 928, 1050, 2232, 2399 cm-1. EM m/z (EI), (%I): 1855 (33)[M], 1275 (50), 720

(67). UV-vis (CH2Cl2), λmax: 494, 396, 314, 245 nm.

General procedure for the preparation of reference compounds: C60 (138.96 mg,

0.193 mmol) was dissolved in chlorobenzene (20 mL) (ultrasound 30 min), compound 9

(97 mg, 0.193 mmol) and N-methylglycine (25.76 mg, 0.289 mmol) were added. The

15

mixture was heated under reflux for 3 h. After the evaporation of the solvent, the

residue was purified by column chromatography on silica gel.

Compound 28: Eluent: Chloroform. Yield 43 %. Mp > 300 ºC. 1H-NMR (300 MHz,

CDCl3, 25ºC): δ= 7.80 (brs, 2H), 7.60 (d, J = 8.51 Hz, 2H), 6.93 (s, 2H), 5.00 (d, J =

9.33 Hz, 1H), 4.96 (s, 1H), 4.29 (d, J = 9.47 Hz, 1H), 4.01-394 (m, 4H), 2.83 (s, 3H),

1.87-1.75 (m, 4H), 1.54-1.49 (m, 4H), 1.36-1.31 (m, 8H), 0.93-0.83 (m, 6H), 0.26 ppm

(s, 9H). 13C-NMR (75 MHz, CDCl3, 25ºC): δ= 156.52, 154.51, 154.30, 153.83, 153.57,

147.72, 147.04, 146.83, 146.73, 146.67, 146.63, 146.56, 146.51, 146.41, 146.36,

146.34, 146.15, 145.93, 145.83, 145.74, 145.67, 145.64, 145.58, 145.10, 145.02,

144.78, 143.55, 143.40, 143.09, 142.98,142.94, 142.67, 142.64, 142.51, 142.43, 142.29,

142.26, 142.09, 141.95, 140.59, 140.56, 140.28, 139.99, 137.70, 137.25, 136.88,

136.29, 136.11, 132.27, 129.67, 123.89, 117.55, 117.13, 114.35, 114.11, 101.47,

100.59, 94.99, 87.04, 83.69, 70.41, 69.93, 69.82, 69.44, 40.44, 32.02, 31.98, 29.68,

29.64, 26.10, 23.05, 14.51, 0.36 ppm. FTIR (KBr): ν= 526, 553, 574, 758, 842, 1161,

1215, 1247, 1377, 1409, 1463, 1490, 1508, 2150, 2779, 2854, 2925, 2949 cm-1. EM m/z

(ESI), (%I): 1249 (M, 40), 1248 (M+, 35), 1024 (10), 924 (23), 817 (8). UV-vis

(CH2Cl2), λmax: 253, 312, 357 nm.

Compound 29: Eluent: Chloroform. Yield 60%. Mp > 300 ºC. 1H-NMR (300 MHz,

CDCl3, 25ºC): δ= 7.81 (brs, 2H), 7.56-7.55 (m, 2H), 6.87 (brs, 4H), 5.02 (d, J = 9.03

Hz, 1H), 4.98 (s, 1H), 4.30 ( d, J = 9.42 Hz, 1H), 3.99-3.95 (m, 8H), 2.86 (s, 3H), 1.86-

1.75 (m, 8H), 1.55-1.50 (m, 8H), 1.49-1.40 (m, 16H), 1.01-0.89 ppm (m, 12H). 13C-

NMR (75 MHz, CDCl3, 25ºC): δ= 155.00, 154.91, 154.08, 153.72, 153.29, 149.46,

147.75, 146.78, 146.39, 146.19, 146.03, 145.69, 145.10, 144.84, 143.05, 142.61,

142.49, 142.35, 132.43, 135.40, 132.03, 129.56, 118.18, 117.75, 117.56, 116.96,

115.45, 113.52, 112.75, 83.75, 77.23, 76.73, 76.28, 74.94, 73.91, 73.12, 69.94, 69,83,

69.75, 69.54, 31.54, 31.51, 29.67, 29.18, 29.14, 29.09, 25.63, 25.59, 22.60, 22.57,

18.67, 18.64, 17.76, 16.22, 16.02, 15.74, 13.98 ppm. FTIR (KBr): ν: 526, 660, 745, 800,

1126, 1310, 1645, 2255 cm-1. UV-vis (CH2Cl2), λmax: 230, 255, 317, 380, 397 nm. EM

m/z (MALDI-TOF): 1290 [M+].

16

Figure S1. Electrostatic potential as calculated by AM1 CIS for the ground and charge-

separated states of 27a-c. The positive charge is represented in red and the negative in

blue.

17

Stabilization of CT States by Solvent and Geometrical Relaxation

Single-point calculations on the relaxed structures of the ground and excited states in

the simulated solvents hexane (ε=2.023), CCl4 (ε=2.229), benzene (ε=2.274), ether

(ε=4.197), chloroform (ε=4.806), methylene chloride (ε=8.930), pyridine (ε=12.40),

acetone (ε=20.56), ethanol (ε=24.55) nitrobenzene (ε=43.82), acetonitrile (ε=35.94) and

dimethyl sulfoxide (ε=46.45) were performed in order to judge the solvent effects on

the relative stabilities of the different states for 27a-c.

Figure S2. Dependence of the calculated heats of formation, ∆Hf, for the discussed

states of 27c on solvent permittivity: ground state (circles), local excited state

(triangles), BCT (squares), CT (rotated squares).

Figure S2 shows the dependence of the calculated heats of formation, ∆Hf, of the

discussed states of 27c on solvent permittivity ((ε-1/(2ε+1)). By optimizing the local-

excited (LE) state, the BCT state and the CT state of 27c, it was possible to determine

the energy levels of the three different Franck-Condon states and get more insight into

the electron-transfer pathway. The calculations reveal that the relative energies of the

different states and conformations and their solvent dependence are reproduced

remarkably well in accordance with the experimental trends. As illustrated in Figure S2,

with higher solvent polarity the energy splitting between the different states increases

significantly whereas their relative energies decrease due to solvent stabilization.

Equally important, one can see that the BCT becomes more and more accessible as the

polarity of the solvent increases. This behavior was also observed in the photophysical

18

experiments. However, no crossing between the CT and BCT state, even in nonpolar

media, was observed during the calculations. The results for the monomer 27a and the

dimer 27b reveal equal solvent dependence of the discussed states. However, in these

two compounds no BCT is present. The heat of formation of the CT states is increasing

almost linearly from monomer to trimer. These trends prove the observations resulting

from the photophysical measurements and confirm the suggested charge-transfer

behavior of the C60-oPPE-exTTF. Thus, the calculations support the hypothesis that in

all solvents an excitation of the triad results in the CT state, which supports our

interpretation of the electron-transfer mechanism.

Calculating the Coulson charge on exTTF and C60 gives a value of 1.0 e- and -1.1 e-,

respectively, for all the triads, indicating complete transfer of one electron from the

donor to the acceptor with some delocalization of the positive charge (4.6 %) into the

bridge. ExTTF is clearly oxidized with the positive charge localized on the sulfur atoms

(0.6 e-), whereas C60 is reduced with the charge being delocalized throughout the carbon

cage. This confirms the one-electron charge transfer from donor to acceptor.

References

[S1] Stockmann, Kurzawa, Fritz, Acar, Schneider, Daub, Engl, Clark, J. Phys. Chem

A 2002, 106, 7958-7970.

[S2] Dewar, M. J. S.; Zoebisch, E.; Healy, E. F.; Stewart, J. J. P. J. Am. Chem. Soc.

1985, 107, 3902. Holder, A. J. In Encyclopedia of Computational Chemistry; Schleyer,

P. v. R., Allinger, N. L., Clark, T., Gasteiger, J., Kollman, P. A., Schaefer, H. F., III,

Schreiner, P. R., Eds.; Wiley: Chichester, 1998; Vol. 1, p 8

[S3] Dewar, M. J. S.; Liotard, D. A. J. Mol. Struct. (THEOCHEM) 1990, 206, 123

[S4] Bondi, A. J. Phys. Chem. 1964, 68, 441

[S5] Local molecular properties and their use in predicting reactivity, B. Ehresmann,

B. Martin, A. H. C. Horn and T. Clark, J. Mol. Model. 2003, 9, 342-347.; QSAR and

QSPR based solely on surface properties?, T. Clark, J. Mol. Graph. Model. 2004, 22,

519-525

19

[S6] T. Clark, Jr-H. Lin, A. H. C. Horn, Parasurf 07Cepos InSilico Ltd., Ryde, UK,

2007 (www.ceposinsilico.com)

[S7] H. Lanig, R. Koenig, T. Clark, Tramp 1.1d 2005.