Photoluminescent Spirosila Compounds
FULL PAPER
quently, diethynylsilane 4 (0.493 g, 1.0 mmol) was added and the mixture
was allowed to gradually warm up to room temperature and was stirred
for an additional hour. 3n Aqueous HCl (5 mL) was added, the reaction
mixture was extracted with diethyl ether (370 mL), and the organic
phase was washed with water and brine. The extract was dried over
MgSO4. The solvent was evaporated in vacuo to give a brown solid. Re-
crystallization from ethanol afforded colorless crystals of 7 (0.34 g, 69%).
1H NMR (250 MHz, CDCl3): d=8.11 (s, 1H), 7.60–7.11 (m, 20H), 7.03 (s,
1H), 3.08–3.02 (m, 1H), 1.56–1.24 (m, 2H), 0.71 ppm (s, 9H); 13C NMR
(62.9 MHz, CDCl3): d=159.6, 157.8, 153.3, 145.6, 144.3, 139.1, 136.9,
136.8, 136.4, 132.0, 131.2, 128.7, 128.5, 128.4, 128.33, 128.25, 128.12,
128.06, 127.2, 127.12, 127.07, 126.7, 41.1, 34.0, 30.5, 29.1 ppm; 29Si NMR
(49.7 MHz, CDCl3): d=À5.14 ppm; elemental analysis calcd (%) for
C36H34Si: C 87.40, H 6.93; found: C 87.32, H 6.68.
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Synthesis of 10: 2,2’-Dibromobiphenyl (0.5 g, 1.6 mmol) and dry diethyl
ether (20 mL) were placed in a 50 mL Schlenk flask and the mixture was
cooled to À788C before nBuLi (23% in hexane, ꢂ2.5m; 1.5 mL,
3.8 mmol) was added dropwise with constant stirring. After completion,
the reaction mixture was warmed up to room temperature and stirred for
20 h to form 2,2’-dilithiumbiphenyl. This solution was added dropwise to
a solution of 1,1-dichlorosilole (0.87 g, 1.9 mmol) in diethyl ether (50 mL)
at room temperature and stirred for 3 d. Water (10 mL) was added and
the organic phase was washed with water (320 mL). After drying over
MgSO4, the solvent was evaporated in vacuo to give a yellow solid that
was purified by column chromatography over silica gel (Rf =0.36,
hexane/acetone=10:1) to give 10 as a greenish yellow crystalline solid
(0.233 g, 26%). 1H NMR (250 MHz, CDCl3): d=7.80–6.59 ppm (m,
28H); 13C NMR (62.9 MHz, CDCl3): d=158.4, 149.9, 139.0, 138.4, 134.6,
133.9, 132.2, 131.1, 129.9, 129.1, 128.1, 127.71, 127.68, 126.6, 125.8,
121.4 ppm; 29Si NMR (49.7 MHz, CDCl3): d=À0.41 ppm; elemental anal-
ysis calcd (%) for C40H28Si·0.75acetone: C 87.45, H 5.64; found: C 87.07,
H 5.67. Element analysis reveals that there are more acetone molecules
in the crystals than those determined by single-crystal X-ray analysis,
which only found 0.25 molecules of acetone. This difference is probably
because not all of the acetone absorbed by the crystals can be detected
by X-ray diffraction.
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1998.
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Synthesis of 12: Tolane (5.33 g, 30 mmol), lithium granules (0.28 g,
40 mmol), and dry diethyl ether (20 mL) were placed in a 250 mL
Schlenk flask. The mixture was stirred at room temperature under argon
for 4 h to give a brown solution and a yellow precipitate. THF (100 mL)
was added to dissolve the precipitate to obtain a solution of dilithium
tetraphenylbutadiene. This solution was added dropwise to a solution of
dichlorosilane 11 (6.83 g, 23.3 mmol) in dry THF (30 mL). Subsequently,
the mixture was refluxed for 3 h to obtain a yellow solution that was
cooled to room temperature and treated with water (70 mL). The reac-
tion mixture was extracted with diethyl ether (370 mL). The organic
phase was washed with water and brine and dried over MgSO4. The sol-
vent was removed in vacuo to give a brown solid that was purified by
column chromatography over silica gel (Rf =0.51, hexane/acetone=20:1)
to give 12 as greenish yellow crystals (3.34 g, 38.5%). 1H NMR
(250 MHz, CDCl3): d=7.30–6.62 (m, 31H), 0.83 ppm (s, 3H; CH3);
13C NMR (62.9 MHz, CDCl3): d=156.0, 141.5, 141.1, 140.8, 139.2, 139.0,
138.7, 137.1, 129.6, 129.5, 129.1, 128.0, 127.9, 127.8, 127.6, 127.5, 127.4,
126.1, 126.0, 125.6, À6.89 ppm; 29Si NMR (49.7 MHz, CDCl3): d=
1.46 ppm; elemental analysis calcd (%) for C43H34Si: C 89.23, H 5.92;
found: C 88.93, H 5.92.
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Crystallographic data: The supplementary crystallographic data for com-
pounds
2 (CCDC-641076), 6 (CCDC-185864), 7 (CCDC-185855), 10
(CCDC-641075), and 12 (CCDC-641074) can be obtained free of charge
ac.uk/data_request/cif.
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pounds, Vol. 3, Wiley, New York, 2001.
[23] D. Yan, A. A. Hess, M. Backer, N. Auner, M. D. Thomson, H. G.
Roskos, W. Fann, unpublished results.
Acknowledgement
We thank the Deutsche Forschungsgemeinschaft (DFG) for financial sup-
port.
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Chem. Eur. J. 2007, 13, 7204 – 7214
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