2-芳基丙硅烷的光化学反应机理  

Photochemical Reaction Mechanism of 2-Aryltrisilanes

作　　者：刘成有[1] 闫锡杰[1] 高玉祥[1] 田贵才[1] 

机构地区：[1]通化师范学院物理系,通化134002

出　　处：《高等学校化学学报》2003年第5期895-899,共5页Chemical Journal of Chinese Universities

基　　金：吉林省教育厅基金

摘　　要：从理论及实验上研究了2-芳基丙硅烷(1)的光物理及光化学特性。结果表明,在极性溶液中观察到的强荧光带来源于分子内电荷转移(ICT);在非极性溶液中,化合物1的光化学反应产物为亚甲硅基并伴随着1,3-甲硅烷基的迁移;而在乙醇-己烷溶液中,光化学反应主要导致Si—Si键的裂解,通过研究光化学反应与温度的关系可确认,亚甲硅基与1,3-甲硅烷基的迁移来源于化合物1的不同电子激发态,非谐振双光子光化学反应(NRTP)结果表明,亚甲硅基迁移来源于化合物1的La电子态。The photophysical and photochemical properties of 2-aryltrisilanes (1) was investigated via theory and experiment. The intense fluorescene band of compound 1 was assigned to the intramolecular charge-transfer (ICT) in a polar solvent. Whereas silylene extrusion and 1,3-silyl migration were the major pho-toreactions of compound 1 resulted from the solvolytic cleavage of the Si-Si bond. The temperature dependence of the products distribution suggested that both the silylene extrusion and 1,3-silyl migration came from the different excited states. The results of the photochemical reaction of compund 1 using a nonresonant two-photo(NRTP) excitation show that the silylene extrusion occurs via the 1La state.

关 键 词：2-芳基丙硅烷 光化学反应机理 分子内电荷转移 非谐振双光子光化学反应 

分 类 号：O627.41[理学—有机化学] O644.1[理学—化学]