R. Grisorio et al. / Tetrahedron 64 (2008) 8738–8745
8745
4.10. 70-Iodo-7%-(5-carbodecaoxy-[2,20]-bithien-50-yl-
ethynyl)-[20,2%]-bis[spiro(cyclohexane-1,90,100,9%-fluorene)]
(15) and 70,7%-bis(5-carbodecaoxy-[2,20]-bithien-50-yl-
ethynyl)-[20,2%]-bis[spiro(cyclohexane-1,90,100,9%-fluorene)]
(SB3)
27.0, 26.0, 25.6, 25.0, 22.8, 22.7, 22.6, 14.2, 14.0 ppm. FTIR (KBr):
¼2925, 2856, 2002 (C^C), 1695 (C]O), 1460, 1270, 1086, 877, 807,
737 cmꢁ1
n
.
Acknowledgements
A mixture of 4 (0.718 g, 1.00 mmol), 10 (0.375 g, 1.00 mmol),
Pd(PPh3)4 (115.5 mg, 0.01 mmol), CuI (19.0 mg, 0.01 mmol) and
diethylamine (15 mL) was refluxed overnight. After cooling the so-
lution to room temperature, diethyl ether (50 mL) was added and
the resulting mixture was washed with water (3ꢂ50 mL) and dried
over Na2SO4. After removing the solvent, compound 11 was isolated
by flash chromatography (SiO2, petroleum ether 40–60 ꢀC/
CH2Cl2¼1:1) in 27% yield as yellow solid and compound SB3 was
isolated by flash chromatography (SiO2, petroleum ether 40–60 ꢀC/
CH2Cl2¼1:2) in 17% yield as pale brown solid. Compound 11:
mp¼110.3–111.9 ꢀC. Anal. Calcd for C57H57IO2S2: C, 70.94; H, 5.95; S,
6.65. Found: C, 70.98; H, 5.91; S, 6.60. 1H NMR (400 MHz, CDCl3):
Dr. Paolo Pesce is gratefully acknowledged for laboratory
assistance.
Supplementary data
This section contains the 1H and 13C{1H} NMR spectra of SB1–4,
and the 1H–1H COSY and 1H–13C HMQC of 1. The EL spectra at dif-
ferent bias and the CV scans of SB1–4 are also reported. Supple-
mentary data associated with this article can be found in the online
References and notes
d
¼8.04 (d, J¼1.3 Hz, 1H), 7.94–7.75 (m, 6H), 7.74–7.62 (m, 4H), 7.60–
7.51 (m, 2H), 7.25 (d, J¼3.8 Hz, 1H), 7.22 (d, J¼3.8 Hz, 1H), 7.19 (d,
J¼3.8 Hz, 1H), 4.32 (t, J¼6.7 Hz, 2H), 2.07–1.72 (m, 22H), 1.50–1.21
(m,14H), 0.91 (t, J¼7.0 Hz, 3H) ppm.13C{1H} NMR (100 MHz, CDCl3):
1. Grimsdale, A. C.; Mu¨llen, K. Macromol. Rapid Commun. 2007, 28, 1676–1702.
2. Leclerc, M. J. Polym. Sci., Part A: Polym. Chem. 2001, 39, 2867–2873.
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5. (a) Chi, C.; Im, C.; Enkelmann, V.; Ziegler, A.; Lieser, G.; Wegner, G. Chem.dEur. J.
2005, 11, 6833–6845; (b) Zojer, E.; Pogantsch, A.; Hennebicq, E.; Beljonne, D.;
Bre´das, J.-L.; Scandiucci de Freitas, P.; Scherf, U.; List, E. J. W. J. Chem. Phys. 2002,
117, 6794–6802; (c) Craig, M. R.; de Kok, M. M.; Hofstraat, J. W.; Schenning,
A. P. H. J.; Meijer, E. W. J. Mater. Chem. 2003, 13, 2861–2862; (d) Cho, S. Y.;
Grimsdale, A. C.; Jones, D. J.; Watkins, S. E.; Holmes, A. B. J. Am. Chem. Soc. 2007,
129, 11910–11911.
d
¼162.1, 155.6, 154.4, 153.4, 143.1, 141.1, 140.1, 138.9, 138.0, 137.8,
137.4, 136.0,134.1,133.7, 132.7,130.6,127.6,126.5,126.3,125.1, 124.3,
124.0, 123.4, 121.6, 120.5, 120.2, 119.9, 96.2, 92.3, 82.3, 65.5, 50.6,
50.5, 35.6, 35.5, 31.9, 29.5, 29.4, 29.3, 28.7, 26.0, 25.4, 22.7, 22.6,
14.1 ppm. Compound SB3: Anal. Calcd for C78H82O4S4: C, 77.31; H,
6.82; S, 10.59. Found: C, 77.35; H, 6.83; S, 10.54. 1H NMR (400 MHz,
CDCl3):
d
¼7.93–7.87 (m, 4H), 7.85 (d, J¼7.9 Hz, 2H), 7.79 (d, J¼7.9 Hz,
2H), 7.73 (d, J¼3.8 Hz, 2H), 7.69 (dd, J¼7.9,1.6 Hz, 2H), 7.58 (dd, J¼7.6,
1.3 Hz, 2H), 7.26 (d, J¼3.8 Hz, 2H), 7.22 (d, J¼3.8 Hz, 2H), 7.19 (d,
J¼3.8 Hz, 2H), 4.32 (t, J¼6.4 Hz, 4H), 2.08,1.98 (m, 8H),1.96–1.73 (m,
16H), 1.50–1.23 (m, 28H), 0.91 (t, J¼7.0 Hz, 6H) ppm. 13C{1H} NMR
6. Mullen, K.; Wegner, G. Electronic Materials: The Oligomer Approach; Wiley-VCH:
Weinheim, 1998.
(100 MHz, CDCl3):
d¼162.1, 154.4, 153.4, 143.2, 141.1, 140.0, 138.0,
7. (a) Culligan, S. W.; Geng, Y.; Chen, S. H.; Klubek, K.; Vaeth, K. M.; Tang, C. W. Adv.
Mater. 2003, 15, 1176–1180; (b) Geng, Y.; Culligan, S. W.; Trajkovska, A.; Wallace,
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J.; Culligan, S. W.; Trajkovska, A.; Chen, S. H.; Rothberg, L. J. Chem. Mater. 2002,
14, 1332–1339; (d) Geng, Y.; Katsis, D.; Culligan, S. W.; Ou, J. J.; Chen, S. H.;
Rothberg, L. J. Chem. Mater. 2002, 14, 463–470; (e) Wong, K.-T.; Chien, Y.-Y.;
Chen, R.-T.; Wang, C.-F.; Lin, Y.-T.; Chiang, H.-H.; Hsieh, P.-Y.; Wu, C.-C.; Chou,
C. H.; Su, Y. O.; Lee, G.-H.; Peng, S.-M. J. Am. Chem. Soc. 2002, 124, 11576–11577.
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Wang, F. S. Synth. Met. 2005, 152, 229–232.
137.5,132.3,130.6,127.6,126.6,125.1,124.3,124.1,123.4,120.6,120.5,
119.9, 96.2, 82.4, 65.5, 50.5, 35.6, 31.9, 29.6, 29.3, 29.2, 28.7, 26.0,
25.5, 22.8, 22.7, 14.1 ppm. FTIR (KBr):
n
¼3067, 2923, 2855, 2188
(C^C), 1703 (C]O), 1471, 1430, 1386, 1089, 824, 741 cmꢁ1
.
4.11. 70-(5-Carbodecaoxy-[2,20]-bithien-50-yl-ethynyl)-7%-(N-
hexylcarbazol-3-yl-ethynyl)-[20,2%]-bis[spiro(cyclohexane-
1,90,100,9%-fluorene)] (SB4)
9. Saragi, T. P. I.; Spehr, T.; Siebert, A.; Fuhrmann-Lieker, T.; Salbeck, J. Chem. Rev.
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A mixture of 11 (0.145 g, 0.15 mmol), 6 (47.7 mg, 0.17 mmol),
Pd(PPh3)4 (20.0 mg, 1.7ꢂ10ꢁ2 mmol) and CuI (3.3 mg,
1.7ꢂ10ꢁ2 mmol) in diethylamine (5 mL) was refluxed overnight.
After cooling the solution to room temperature, diethyl ether
(50 mL) was added and the resulting mixture was washed with
water (3ꢂ30 mL) and dried over Na2SO4. After removing the sol-
vent, the crude product was purified by flash chromatography
(SiO2, petroleum ether 40–60 ꢀC/CH2Cl2¼3:1) to give SB4 in 93%
yield as yellow solid. Anal. Calcd for C77H77NO2S2: C, 83.12; H, 6.98;
N, 1.26; S, 5.76. Found: C, 83.18; H, 6.94; N, 1.26; S, 5.77. 1H NMR
(400 MHz, CDCl3):
d
¼8.38 (s, 1H), 8.15 (d, J¼7.6 Hz, 1H), 7.98–7.91
(m, 3H), 7.89 (s, 1H), 7.84 (d, J¼7.9 Hz, 2H), 7.78 (dd, J¼7.9, 3.5 Hz,
2H), 7.75–7.67 (m, 3H), 7.64 (d, J¼7.9 Hz, 1H), 7.56 (d, J¼8.3 Hz, 1H),
7.53 (pt, J¼7.9 Hz, 1H), 7.47–7.39 (m, 2H), 7.31 (d, J¼7.6 Hz, 1H), 7.26
(d, J¼3.5 Hz, 1H), 7.22 (d, J¼3.5 Hz, 1H), 7.19 (d, J¼3.5 Hz, 1H), 4.34–
4.31 (m, 4H), 2.10–1.69 (m, 24H), 1.52–1.15 (m, 20H), 0.95–0.84 (m,
14. Grisorio, R.; Piliego, C.; Fini, P.; Cosma, P.; Mastrorilli, P.; Gigli, G.; Suranna, G. P.;
6H) ppm. 13C{1H} NMR (100 MHz, CDCl3):
d¼162.1, 154.4, 154.3,
Nobile, C. F. J. Phys. Chem. C 2008, 112, 7005–7014.
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J. Am. Chem. Soc. 2000, 122, 1820–1821.
153.4, 153.4, 143.2, 141.3, 140.8, 140.7, 140.1, 139.1, 138.4, 138.0, 134.1,
132.7, 132.3,130.7, 130.6, 129.3,127.7, 127.6, 126.6,126.5,126.1, 125.1,
124.2, 124.1, 124.0, 123.4, 122.9, 122.5, 122.1, 120.5, 120.4, 120.3,
119.9, 119.8, 119.3, 108.9,108.8, 96.3, 91.0, 88.6, 82.4, 65.5, 50.5, 50.4,
43.2, 35.7, 35.6, 31.9, 31.6, 29.7, 29.6, 29.3, 29.2, 29.1, 29.0, 28.7, 27.2,