H]+:
145.7 (2C), 145.6, 145.5, 144.9 (2C), 143.4, 142.9, 142.8, 142.5,
142.4, 142.3, 142.1, 142.0, 141.5, 140.6, 138.9, 137.5 (29 signals
from the C60 core), 135.0 (–CQ, Ar), 134.5 (–CQ, Ar), 133.9
(–CQ, Ar), 132.3 (–CQ, Ar), 128.4 (–CQ, Ar), 127.4 (–CQ, Ar),
115.0 (–CQ, Ar), 114.5 (–CQ, Ar), 87.0 (–CR), 85.9 (–CR),
68.5 (CH2–Ar), 68.4, 66.8 (C-Ar in the C60 core), 61.1, 50.4,
32.6 (O–CH2), 32.1 (CH2), 29.6 (CH2), 29.5 (CH2),
29.4 (CH2), 26.3 (CH2), 22.9 (CH2), 14.4 (CH3); HRMS
(APPI-TOF): m/z calc. for C83H28O [M + H]+: 1041.2213,
found 1041.2213.
(APPI–TOF): m/z calc. for C81H26OS [M
+
1047.1777, found 1047.178.
Synthesis of compound 6
See the general procedure for the addition of C60 to terminal
alkynes. The materials used were 1-ethynyl-4-(octyloxy)-
benzene (50 mg, 0.22 mmol), C60 (313 mg, 0.43 mmol), THF
(86.8 mL), LHMDS (0.49 mL, 0.43 mmol) and 2-(bromo-
methyl)thiophene11 (1.54 g, 8.68 mmol). The crude product
was purified by flash chromatography on silica gel with
hexanes to 40% CS2/hexanes as eluents to afford compound
6 (27 mg, 12% yield) as a brown powder: mp 4 300 1C;
1H NMR (CDCl3, 400 MHz): 7.97 (s, 1H), 7.47 (d, J = 8.6 Hz,
2H), 7,29 (d, J = 5.6 Hz, 1H), 7.05 (t, J = 4.2 Hz, 1H), 6.88
(d, J = 8.6 Hz, 2H), 5.18 (s, 2H), 3.95 (t, J = 6.5 Hz, 2H), 1.73
(m, 2H), 1.25 (m, 10H), 0.86 (m, 3H); 13C NMR (CDCl3, 100
MHz): 160.3, 155.4, 154.4, 147.9 146.7 146.6, 146.5 (2C),
146.4, 146.0, 145.7, 145.6, 145.3, 144.8 (2C) 143.3 (2C), 142.9
(2C), 142.5, 142.4, 141.9, 141.8, 141.7 (2C) (25 signals from the
C60 core), 139.8 (–CQ, Ar), 139.4 (–CQ, Ar), 139.1 (–CQ,
Ar), 136.1 (–CQ, Ar), 135.4 (–CQ, Ar), 134.7 (–CQ, Ar),
131.3 (–CQ, Ar), 131.3 (–CQ, Ar), 130.3, 127.2, 127.1, 126.0,
125.5, 125.1,124.4, 114.7, 77.6, 77.3, 77.0, 69.5, 68.5 (CH2–Ar),
68.2, 32.1 (O–CH2), 29.7 (CH2), 29.6 (CH2), 29.5 (CH2), 29.3
(CH2), 26.3 (CH2), 23.0 (CH2), 14.4 (CH3); HRMS
(APPI–TOF): m/z calc. for C81H26OS [M + H]+:1047.1777,
found 1047.1765.
Synthesis of compound 4
See the general procedure for the addition of C60 to terminal
alkynes. The materials used were 1-ethynyl-4-(octyloxy)-
benzene (50 mg, 0.22 mmol), C60 (313 mg, 0.43 mmol), THF
(86.8 mL), LHMDS (0.49 mL, 0.43 mmol) and 4-(methylthio)-
benzyl bromide (1.89 g, 8.68 mmol). The crude product was
purified by flash chromatography on silica gel with hexanes to
40% CS2/hexanes as eluents to afford compound 4 (22 mg,
10% yield) as a brown powder: mp 4 300 1C; 1H NMR
(CDCl3, 400 MHz): 7.69 (d, J = 8.6 Hz, 2H), 7.43 (d, J =
8.6 Hz, 2H), 7.17 (d, J = 8.4 Hz, 2H), 6.95 (d, J = 8.6 Hz,
2H), 5.17 (s, 2H) 4.01 (t, J = 6.5 Hz, 2H), 2.44 (s,3H), 1.82
(m, 2H), 1.30 (m, 10H), 0.90 (m, 3H); 13C NMR (CDCl3,
100 MHz): 154.3, 154.2, 146.8, 146.7, 146.6, 146.5, 146.2, 145.7
(3C), 145.4, 145.0, 143.4, 143.0, 142.9 (2C), 142.5, 142.4, 142.3,
142.1, 142.0, 141.6, 140.6 (23 signals from the C60 core), 139.1
(–CQ, Ar), 135.1 (–CQ, Ar), 134.5 (–CQ, Ar), 133.9 (–CQ,
Ar), 132.6 (–CQ, Ar), 129.8 (–CQ, Ar), 126.8 (–CQ, Ar),
126.2 (–CQ, Ar), 115.0, 114.5, 87.0 (–CR), 68.4 (CH2–Ar),
67.0, 66.8 (C-Ar in the C60 core), 49.9 (S–CH3), 32.1 (O–CH2),
29.7 (CH2), 29.6 (CH2), 29.5 (CH2), 26.4 (CH2), 23.0 (CH2),
15.9 (CH2), 14.4 (CH3); HRMS (APPI-TOF); m/z calc. for
C84H30OS [M + H]+: 1087.2090, found 1087.2106.
Synthesis of compound 7
See the general procedure for the addition of C60 to terminal
alkynes. The materials used were 1-ethynyl-4-(octyloxy)-
benzene (50 mg, 0.22 mmol), C60 (312 mg, 0.43 mmol), THF
(86.8 mL), LHMDS (0.49 mL, 0.43 mmol) and pentafluoro-
benzyl bromide (1.31 mL, 8.68 mmol). The crude product was
purified by flash chromatography on silica gel with hexanes to
20% CS2/hexanes as eluents to afford compound 7 (97 mg,
40% yield) as a brown powder: mp 4 300 1C; 1H NMR
(CDCl3, 400 MHz): 7.74 (d, J = 8.6 Hz, 2H), 6.98 (d, J =
8.6 Hz, 2H), 5.31 (s, 2H), 4.03 (t, J = 6.6 Hz, 2H), 1.83
(m, 2H), 1.31 (m, 10H), 0.89 (m, 3H); 13C NMR (CDCl3,
100 MHz): 153.5, 152.8, 146.8 (2C), 146.6, 146.5, 146.2, 145.8,
145.7, 145.2, 145.1, 145.0, 144.8, 143.5, 143.3, 142.9, 142.6,
142.4, 142.3, 142.0, 141.9, 141.6, 140.6, 139.5 (24 signals from
the C60 core), 134.4 (–CQ, Ar), 133.9 (–CQ, Ar), 115.0 (–CQ,
Ar), 114.1 (–CQ, Ar), 87.3 (–CR), 86.3 (–CR), 68.5
(CH2–Ar), 65.2 (C-Ar in the C60 core), 36.8 (O–CH2), 32.1
(CH2), 31.8 (CH2), 29.6 (CH2), 29.5 (CH2), 26.3 (CH2), 22.9
(CH2), 14.4 (CH3); 19F NMR (CDCl3, 376 MHz): À139.4 (dd,
J1 = 14.8 Hz, J2 = 7.8 Hz, 2F), À153.7 (t, J = 21.3 Hz, 1F),
À161.5 (m, 2F); HRMS (APPI-TOF) m/z calc. for C83H23F5O
[M + H]+: 1131.1742, found 1131.1722.
Synthesis of compound 5
See the general procedure for the addition of C60 to terminal
alkynes. The materials used were 1-ethynyl-4-(octyloxy)-
benzene (50 mg, 0.22 mmol), C60 (313 mg, 0.43 mmol), THF
(86.8 mL), LHMDS (0.49 mL, 0.43 mmol) and 3-(bromo-
methyl)thiophene11 (1.54 g, 8.68 mmol). The crude product
was purified by flash chromatography on silica gel with
hexanes to 40% CS2/hexanes as eluents to afford compound
5 (46 mg, 20% yield) as a brown powder: mp 4 300 1C;
1H NMR (CDCl3, 400 MHz): 8.00 (s, 1H), 7.50 (d, J = 8.6 Hz,
2H), 7.45 (d, J = 1.6 Hz, 1H), 7.32 (m, 1H), 6.88 (d, J =
8.6 Hz, 2H), 5.00 (s,2H), 3.96 (t, J = 6.5 Hz, 2H), 1.74
(m, 2H), 1.26 (m, 10H), 0.87 (m, 3H); 13C NMR (CDCl3,
100 MHz): 160.3, 155.5, 154.2, 147.6 (2C), 146.4, 146.3, 146.2,
146.1 (2C), 145.8, 145.4, 145.3, 145.2, 145.0, 144.6, 144.5 (2C),
143.1, 142.6, 142.2, 142.1, 141.6, 141.5 (2C) (25 signals from
the C60 core), 139.6 (–CQ, Ar), 138.8 (–CQ, Ar), 137.5 (–CQ,
Ar), 136.1 (–CQ, Ar), 134.8 (–CQ, Ar), 134.5 (–CQ, Ar),
131.0 (–CQ, Ar), 130.9 (–CQ, Ar), 130.8, 125.8, 125.4,
124.4, 114.5, 68.2 (CH2–Ar), 67.9 (C-Ar in the C60 core),
31.8 (O–CH2), 29.7 (CH2), 29.3 (CH2), 29.2 (CH2), 29.0
(CH2), 25.0 (CH2), 22.7 (CH2), 14.2 (CH3); HRMS
Synthesis of compound 8
See the general procedure for the addition of C60 to terminal
alkynes. The materials used were 1-ethynyl-4-(octyloxy)-
benzene (50 mg, 0.22 mmol), C60 (312 mg, 0.43 mmol), THF
(86.8 mL), LHMDS (0.49 mL, 0.43 mmol) and pentabromo-
benzyl bromide (3.0 g, 5.4 mmol). The crude product was
c
946 New J. Chem., 2011, 35, 942–947
This journal is The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2011