論文 - 熊谷　純

Electronec Structure of Oligosilane and Polysilane Radical Anions As Studied by Electron Spin Resonance and Electronic Absorption Spectroscopy 査読有り

J. Kumagai, H. Yoshida, H. Koizumi, T. Ichikawa

J. Phys. Chem.   98 巻 ( 50 ) 頁： 13117-13122   1994年12月

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担当区分：筆頭著者   記述言語：英語   掲載種別：研究論文（学術雑誌）  

The electron spin resonance (ESR) and the electronic absorption spectra of poly(cyclohexylmethylsilane) and poly(methylphenylsilane) radical anions in a cryogenic 2-methyltetrahydrofuran solid have been compared with those of permethyloligosilanes [Si-n(CH3)(2n+2), n = 4-6] for elucidating the electronic structure of polysilane radical anions. The spectra of the polysilane radical anions are very similar to each other and also to those of the oligosilane radical anions in which an unpaired electron occupies not an antibonding sigma(not asymptotic to)(sp) orbital but a pseudo-pi(p) orbital composed of antibonding Si-Si and antibonding Si-C orbitals. The polysilane radical anions show axially symmetric ESR spectra with g(perpendicular to) = 2.0023 and g(parallel to) = 2.0064 and the electronic absorption spectra composed of UV and near-IR bands. Analysis of the ESR and the absorption spectra shows that the unpaired electron of the polysilane radical anions is not delocalized all over the polymer chain but is confined in only a part of the polymer chain, probably around the elongated Si-Si bond of a branched polymer chain.

DOI： 10.1021/j100101a005