Synthesis and absorption/emission properties of novel poly(silylenearylenevinylene)s |
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Authors: | Giseop Kwak Ken-Ichi Sumiya Fumio Sanda Toshio Masuda |
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Institution: | Department of Polymer Chemistry, Graduate School of Engineering, Kyoto University, Kyoto 606-8501, Japan |
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Abstract: | Polymerization of p-(dimethylsilyl)phenylacetylene in toluene at 25 and 80 °C with RhI(PPh3)3 catalyst afforded highly regio- and stereoregular poly(dimethylsilylene-1,4-phenylenevinylene)s cis- and trans-poly( 1a )s] containing 98% cis- and 99% trans-vinylene moieties, respectively. The trans-type polymers exhibited redshifts and hyperchromic effects in the ultraviolet–visible spectrum as compared with the cis-type counterparts. Photoirradiation of cis- and trans-poly( 1a )s gave cis-rich mixtures at equilibrium states. The trans and cis polymers exhibited different emission properties, for example—trans polymer, emissn λmax = 400 nm, quantum yield: 3.4 × 10−3 and cis polymer, emissn λmax = 380 nm, quantum yield: 1.5 × 10−3. Besides poly( 1a ), poly(dimethylsilylenearylenevinylene)s containing biphenylene and phenylenesilylenephenylene units poly( 3 )] were prepared. The extent of conjugation in these polymers decreased in the orders of biphenylene > phenylene > phenylenesilylenephenylene as well as trans-vinylene > cis-vinylene. The quantum yield of the trans-rich polymer with biphenylene moiety was fairly large and 0.15. Polyaddition of 1,4-bis(dimethylsilyl)benzene and three types of diethynylarenes (4,4′-diethynylbiphenyl, 2,7-diethynylfluorene, and 2,6-diethynylnaphthalene) catalyzed by RhI(PPh3)3 provided novel regio- and stereoregular polymers poly( 6 )]. These polymers displayed blue light emission with high quantum yields (4–81%). © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3615–3624, 2003 |
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Keywords: | poly(silylenearylenevinylene) conjugated polymers heteroatom-containing polymers absorption luminescence quantum yield geometric structure |
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