Fullerene–Foldamer Stacking Interactions
FULL PAPER
crude product was dissolved in THF (5 mL). The solution obtained was
added dropwise to a solution of 10 (0.53 g, 0.80 mmol) and triethylamine
(4.00 mL, 29.1 mmol) in THF (20 mL) and the mixture was stirred at
room temperature for 2 h. After removal of the solvent under reduced
pressure, the residue was redissolved in chloroform (40 mL). This solu-
tion was washed with dilute hydrochloric acid (1n, 20 mL), saturated
sodium hydrogen carbonate solution (20 mL), water (20 mL), and brine
(20 mL), and then dried over sodium sulfate. After removal of the sol-
vent in a rotary evaporator, the residue obtained was subjected to
column chromatography (AcOEt/chloroform, 3:2, v/v) to give 3 as a pale
yellow solid (0.47 g, 78%). 1H NMR (CDCl3): d=9.26 (d, J=6.3 Hz,
2H), 8.95 (d, J=8.1 Hz, 2H), 8.84–8.83 (m, 4H), 8.17 (d, J=6.9 Hz, 2H),
8.03 (t, J=6.9 Hz, 2H), 7.95–7.87 (m, 4H), 7.59 (d, J=5.4 Hz, 2H), 7.26
(t, J=5.4 Hz, 2H), 6.98–6.89 (m, 4H), 3.25 (t, J=5.1 Hz, 4H), 3.11 (t, J=
5.1 Hz, 4H), 2.30 (s, 6H), 1.44–1.12 (m, 48H), 0.87–0.77 ppm (m, 12H);
13C NMR (CDCl3): d=170.4, 161.2, 161.0, 159.5, 159.2, 158.6, 155.9,
154.7, 151.4, 144.7, 143.8, 141.5, 135.0, 134.8, 134.5, 134.4, 133.3, 133.2,
129.2–129.1 (m), 126.0, 125.8, 125.4, 125.3, 125.0–124.9 (m), 124.7, 124.5,
124.4, 123.3–123.2 (m), 122.8, 122.7, 122.6, 122.5, 121.0, 119.9, 119.8,
115.2, 114.9, 49.3, 45.2, 31.8, 31.7, 29.7, 29.3, 29.3, 29.0, 28.6, 27.3, 27.1,
26.5, 22.7, 22.6, 21.4, 14.1 ppm; 19F NMR (CDCl3): d=ꢀ105.0 (br, 1F),
ꢀ115.1 (br, 2F), ꢀ126.8 (br, 2F), ꢀ145.6 ppm (br, 2F); MS (MALDI-
TOF): m/z: 1526.7 [M+H]+; HRMS (MALDI-TOF): calcd for
C84H99F7N9O10: 1526.7349 [M]+; found: 1526.7397.
119.0, 118.8, 115.3, 115.0, 49.3, 45.2, 31.8, 31.7, 30.3, 29.4, 29.3, 29.1, 28.6,
27.5, 27.1, 26.6, 22.7, 22.6, 21.5, 14.1 ppm; 19F NMR (CDCl3): d=ꢀ115.16
to ꢀ116.5 (br, 4F), ꢀ126.9 (br, 1F), ꢀ149.7 ppm (br, 2F); MS (MALDI-
TOF): m/z: 1518.8 [M+Na]+; HRMS (MALDI-TOF): calcd for
C84H100F7N9O8Na: 1518.7393 [M+Na]+; found: 1518.7363.
Acknowledgements
We thank the National Natural Science Foundation (Nos. 20332040,
20425208, 20572126, 20621062, 20672137) and the National Basic Re-
search Program of China (2007CB808000) for financial support.
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The following two compounds were prepared from the appropriate start-
ing materials according to similar procedures.
Compound4 : 1H NMR ([D6]DMSO): d=10.86 (br, 2H), 10.38 (br, 4H),
10.36 (br, 4H), 10.32 (br, 4H), 8.68 (s, 1H), 8.38 (d, J=5.7 Hz, 4H), 8.26
(d, J=8.1 Hz, 2H), 7.95–7.83 (m, 12H), 7.79 (t, J=7.2 Hz, 1H), 7.54–7.50
(m, 8H), 7.47 (t, J=7.5 Hz, 4H), 7.38 (t, J=9.6 Hz, 4H), 7.21–7.16 (m,
4H), 3.35 (br, 8H), 3.17 (br, 8H), 3.17 (s, 12H), 1.57–1.08 (m, 96H),
0.87–0.78 ppm (m, 24H); 13C NMR ([D6]DMSO): d=169.2, 165.2, 165.1,
162.6–162.2 (m), 158.0, 155.8–155.6 (m), 154.6, 152.4, 134.6, 133.6, 133.5,
133.1, 133.0, 132.5–132.4 (m), 125.6–125.3 (m), 124.8–124.4 (m), 123.7–
123.5 (m), 122.9–122.7 (m), 122.3–122.0 (m), 116.0, 115.7, 48.5, 44.4, 31.2,
29.0, 28.8–28.5 (m), 28.1–27.9 (m), 27.1–27.0 (m), 26.5–26.4 (m), 25.9–25.8
(m), 22.1, 20.7, 13.9 ppm; 19F NMR ([D6]DMSO): d=ꢀ115.4 (br, 4F),
ꢀ120.4 (br, 2F), ꢀ122.0 to ꢀ122.2 (br, 4F), ꢀ136.1 to ꢀ136.3 ppm (br,
4F); MS (MALDI-TOF): m/z: 3145.1 [M+Na]+; HRMS (MALDI-TOF):
calcd for C176H203F14N18O18: 3122.5300 [M+H]+; found: 3122.5293.
1
Compound5 : H NMR ([D6]DMSO): d=11.01 (br, 3H), 10.37–10.31 (m,
18H), 8.85 (s, 3H), 8.37 (d, J=5.7 Hz, 6H), 7.93 (t, J=6.0 Hz, 6H), 7.87
(t, J=7.2 Hz, 12H), 7.52–7.50 (m, 12H), 7.46 (t, J=7.5 Hz, 6H), 7.37 (t,
J=9.6 Hz, 6H), 7.20–7.16 (m, 6H), 3.36 (br, 12H), 3.16 (br, 12H), 2.34
(s, 18H), 1.53–1.12 (m, 144H), 0.83–0.80 ppm (m, 36H); 13C NMR
([D6]DMSO): d=174.3, 170.7, 169.7, 167.6–167.3 (m), 162.7, 160.6–160.5
(m), 159.4, 157.2, 140.3, 138.8, 138.7, 138.3, 138.2, 137.8–137.6 (m), 130.7–
130.4 (m), 130.1–129.5 (m), 129.0–128.7 (m), 128.0–127.9 (m), 127.4–127.2
(m), 121.2, 120.9, 49.2, 36.4, 34.0, 34.2–33.5 (m), 33.3–33.1 (m), 32.4–32.1
(m), 31.7–31.5 (m), 31.2–31.0 (m), 27.3, 25.9, 19.1 ppm; 19F NMR
([D6]DMSO): d=ꢀ115.4 (s, 6F), ꢀ120.0 (s, 3F), ꢀ122.0 (d, J=9.6 Hz,
6F), ꢀ136.1 ppm (t, J=9.0 Hz, 6F); MS (MALDI-TOF): m/z: 4647.3
[M+H]+; elemental analysis calcd for C261H300F21N27O27·H2O: C 67.20, H
6.54, N 8.11; found: C 66.92, H 6.55, N 7.90.
Compound11 : Pd/C (10%, 30 mg) was added to a solution of compound
3 (0.31 g, 0.20 mmol) in THF (40 mL). The suspension was stirred under
1 atmosphere of hydrogen gas at room temperature for 24 h. The solid
was then filtered off and the solution was concentrated in a rotary evapo-
rator. The residue obtained was purified by flash chromatography
(AcOEt/chloroform, 3:2, v/v) to give 11 as a white solid (0.28 g, 95%).
1H NMR (CDCl3): d=9.02 (d, J=10.5 Hz, 2H), 8.84 (d, J=10.5 Hz, 2H),
8.67 (d, J=10.5 Hz, 2H), 8.25 (d, J=6.6 Hz, 2H), 8.08–8.01 (m, 4H), 7.81
(d, J=5.1 Hz, 2H), 7.74 (d, J=5.1 Hz, 2H), 7.33 (t, J=7.8 Hz, 2H), 7.16
(d, J=5.1 Hz, 2H), 6.98–6.95 (m, 4H), 4.126 (br, 2H), 3.37 (t, J=5.1 Hz,
4H), 3.16 (t, J=5.1 Hz, 4H), 2.25 (s, 6H), 1.51–1.14 (m, 48H), 0.87–
0.78 ppm (m, 12H); 13C NMR (CDCl3): d=170.3, 161.7, 161.1, 159.4,
156.0, 154.8, 151.5, 144.0, 140.8, 135.2, 135.1, 134.5, 134.4, 133.5, 125.9,
125.8, 125.5, 125.2, 125.0, 123.6, 123.5, 123.4, 122.8, 122.6, 121.2, 120.4,
Chem. Eur. J. 2007, 13, 9990 –9998
ꢀ 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
9997