A Soluble Donor–Acceptor Double-Cable Polymer
525
the suspension was filtered and the acetone was removed under reduced pressure. The residue, treated
with 10cm3 of brine, was extracted twice with CH2Cl2. The combined organic layers were dried
(MgSO4), the solvent was evaporated, and the residue was purified by flash column chromatography
(SiO2, petroleum ether:ethyl acetate ¼ 9:1) giving 532mg of 6 (81%) as a pale, oily compound. TLC
(petroleum ether:ethyl acetate ¼ 9:1): Rf ¼ 0.64; IR (KBr): ꢁꢀ ¼ 3039, 2941, 2921, 2869, 2849, 1703,
1602, 1508, 1477, 1309, 1259, 1238, 1214, 1156, 1036cmÀ 1; 1H NMR (200MHz, CDCl3): ꢀ ¼ 9.88
(s, 1H), 7.82 (d, J ¼ 9 Hz, 2H), 7.61 (dd, J ¼ 1.2 Hz, J ¼ 3 Hz, 1H), 7.46 (dd, J ¼ 1.2 Hz, J ¼ 5 Hz, 1H),
7.31 (m, 2H), 7.05 (dd, J ¼ 2 Hz, J ¼ 7.4 Hz, 1H), 6.99 (d, J ¼ 9 Hz, 2H), 6.88 (d, J ¼ 9 Hz, 1H), 4.00
(m, 4H), 2.57 (t, J ¼ 7.6Hz, 2H), 1.84–0.70 (m, 27H) ppm; 13C NMR (62.5MHz, CDCl3): ꢀ ¼ 190.8,
164.2, 154.0, 138.6, 135.0, 132.0, 129.7, 128.6, 127.9, 124.8, 124.0, 122.8, 114.7, 112.4, 68.5, 68.4,
35.1, 31.9, 31.8, 29.5, 29.3, 29.2, 29.0, 25.9, 22.7ppm.
Fulleropyrrolidine-thiophene 7 (C95H49O2NS)
A mixture of 250 mg of aldehyde 6 (0.48 mmol), 690 mg of C60 (0.96 mmol), and 85 mg of N-
methylglycine (0.96 mmol) in 300 cm3 of chlorobenzene was heated to reflux temperature for 5 h.
After cooling to room temperature, the mixture was concentrated under reduced pressure to about
30cm3 and loaded on top of a SiO2 chromatography column. Elution with toluene:petroleum
ether ¼ 6:4 gave first unreacted C60 and then 640 mg of fulleropyrrolidine 7 (52%) as a brown solid.
IR (KBr): ꢁꢀ ¼ 3238, 2923, 1639, 1617, 1247, 620 cmÀ 1; UV-VIS (CH2Cl2): ꢂ(") ¼ 232 (106154), 256
(122733), 306 (42227), 327 (32767), 430 (4069), 700 (870) nm (dm3 molÀ 1 cmÀ 1); 1H NMR
(250 MHz, CDCl3=CS2): ꢀ ¼ 7.62 (m, 2H), 7.47 (dd, J ¼ 1.2 Hz, J ¼ 3 Hz, 1H), 7.32 (dd, J ¼ 1.2 Hz,
J ¼ 5 Hz, 1H), 7.16 (m, 2H), 6.94 (dd, J ¼ 2 Hz, J ¼ 8.2 Hz, 1H), 6.85 (d, J ¼ 9 Hz, 2H), 6.75 (d,
J ¼ 9 Hz, 1H), 4.93 (d, J ¼ 9.5 Hz, 1H), 4.84 (s, 1H), 4.22 (d, J ¼ 9.5Hz, 1H), 3.94 (m, 4H), 2.76 (s,
3H), 2.52 (t, J ¼ 7.5, 2H), 1.88–0.87 (m, 27H)ppm; 13C NMR (62.5 MHz, CDCl3=CS2): ꢀ ¼ 14.2,
22.8, 26.1, 26.2, 29.3, 29.4, 29.6, 31.8, 32.0, 35.2, 39.9, 67.7, 68.3, 68.7, 69.8, 83.0, 112.2, 114.4,
122.8, 123.9, 124.6, 127.8, 128.4, 129.6, 130.2, 134.7, 135.6, 136.4, 136.6, 138.4, 139.4, 139.8, 140.0,
140.02, 141.4, 141.5, 141.7, 141.8, 141.9, 141.9, 142.1, 142.4, 142.5, 142.8, 143.0, 144.2, 144.5, 144.5,
145.0, 145.1, 145.3, 145.4, 145.4, 145.6, 145.8, 146.0, 146.0, 146.2, 146.2, 146.3, 146.6, 147.1, 153.5,
153.0, 156.2, 159.0ppm. MS (MALDI-TOF): m=z ¼ 1268 (Mþ H)þ .
Polymerization
To a solution of 0.395 g of (3-(40-(100, 400, 700-trioxaoctyl)phenyl)thiophene) (1.42 mmol) and 0.200 g of
7 (0.157mmol) in 12cm3 of CHCl3 a slurry of 1.54 g of FeCl3 (9.5mmol) in 20cm3 of CHCl3 was
added over 5 h at room temperature. The polymer was obtained as a dark solid after precipitation from
methanol. The polymer was carefully dedoped by conc. NH4OH followed by 0.05M EDTA, then lower
molecular weight and irregular compounds were removed by Soxhlet extraction with diethyl ether. To
remove any remaining monomer, the precipitated polymer was slurried in toluene at room temperature
and filtered to provide 222 mg (36 w=w%) of pure polymer 1. The purity was checked by size exclusion
chromatography, to establish that no monomers were remaining in the polymer.
Photoinduced Absorption
PIA spectra of the polymer films were taken using the 476nm line of an Arþ laser beam as an
excitation source, with a typical intensity of 40mW on a 4 mm diameter spot. The pump beam was
modulated mechanically at a frequency of 210Hz and the changes in the white light (120W tungsten-
halogen lamp) probe beam transmission ( À ꢁT) were detected, after dispersion with a 0.3 m mono-
chromator, in the range from 0.55 to 2.15 eV by a Si–InGaAsSb sandwich detector. The detector signals
were recorded phase sensitively with a dual-phase lock-in amplifier. The probe light transmission