Photochemical Properties of Network and Branched Polysilanes

Akira Watanabe, Hajime Miike, Yasuaki Tsutsumi, Minoru Matsuda

Research output: Contribution to journalArticlepeer-review

70 Citations (Scopus)


Linear, branched, and network polysilanes were synthesized by the copolymerization of dichloromethylphenylsilane and trichlorophenylsilane. The influence of the Si-skeleton on absorption and emission spectra was investigated. The sharp σ-σ* absorption band (λmax 334 nm) of linear poly-(methylphenylsilylene) changed into a broad one with branching. The shift of the absorption edge to a longer wavelength (410 nm) suggests that the increase of σ-conjugation is due to the silicon network structure. The sharp emission (λmax 355 nm) of linear poly(methylphenylsilylene) also shifted to the broad emission (λmax 471 nm) for network poly(phenylsilyne). The intermediates formed during the photodegradation of polysilanes with various Si-skeletons were investigated by flash photolysis. The time-resolved absorption spectra exhibited the absorption bands of a silyl radical and silylenes. The significant influence of the excitation wavelength was observed. Silylene was produced effectively by the excitation at shorter wavelength (π-π* excitation). The transient absorption spectrum for network poly(phenylsilyne) suggested the formation of a silylsilylene in the silicon network structure. The absorption of the silylsilylene appeared at longer wavelength (λmax 550 nm) compared to that of low molecular weight silylene (λmax 480 nm).

Original languageEnglish
Pages (from-to)2111-2116
Number of pages6
Issue number8
Publication statusPublished - 1993 Jan 1

ASJC Scopus subject areas

  • Organic Chemistry
  • Polymers and Plastics
  • Inorganic Chemistry
  • Materials Chemistry


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