期刊
CHEMISTRY-AN ASIAN JOURNAL
卷 3, 期 8-9, 页码 1456-1464出版社
WILEY-BLACKWELL
DOI: 10.1002/asia.200800125
关键词
conjugation; density functional calculations; fluorescence; polymers; silicon
资金
- Ministry of Education, Culture, Sports, Science, and Technology, Japan [19675001]
- SORST, Japan Science and Technology Agency
We report the synthesis and photophysical properties of poly(aryleneethynylene)s (PAEs) containing disilyl- or tetrasilyl-substituted phenylene as the key building unit. The fluorescence spectra of one of the PAEs, consisting of the diethynylbis(trimethylsilyl)phenylene and fluorenylene units, shows an intense blue emission with the maximum at 428 nm. The absolute quantum yield (0,) and the fluorescence lifetime (Phi(F)) are 0.92 and 0.39 ns, respectively. The calculated radiative decay rate constant (k(r)) from the singlet excited state, based on Phi(F) and tau(s), is 2.4 x 10(9) s(-1), which is extremely large for organic molecules. A series of silyl-substituted PAEs, including a tricyclic tetrasilylphenylene-containing polymer, also show intense emissions with large k(r) values. Theoretical calculations of the model systems with the bis(phenylethynyl)benzene skeleton reveal the general substituent effect of the silyl groups attached to the PAE skeleton.
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