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Disilylphenylene and Tetrasilylphenylene as a New Building Unit for Highly Fluorescent Poly(aryleneethynylene)s
Author(s) -
Iida Azusa,
Nagura Kazuhiko,
Yamaguchi Shigehiro
Publication year - 2008
Publication title -
chemistry – an asian journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.18
H-Index - 106
eISSN - 1861-471X
pISSN - 1861-4728
DOI - 10.1002/asia.200800125
Subject(s) - quantum yield , silylation , trimethylsilyl , substituent , fluorescence , molecule , excited state , phenylene , photochemistry , chemistry , benzene , yield (engineering) , singlet state , polymer , materials science , medicinal chemistry , organic chemistry , atomic physics , physics , catalysis , quantum mechanics , metallurgy
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 ( Φ F ) and the fluorescence lifetime ( τ s ) are 0.92 and 0.39 ns, respectively. The calculated radiative decay rate constant ( k r ) from the singlet excited state, based on Φ F and τ s , is 2.4×10 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.