SYNTHESIS AND OPTICAL-ELECTRONIC PROPERTIES OF POLY[METHYLTETRAPHENYLPHENYLSILYLENE-CO-BIS(METHYLPHENYLSILYL)ACETYLENE]  

作　　者：冯圣玉 

机构地区：[1]School of Chemistry and Chemical Engineering, Shandong University, Jinan 250100, China

出　　处：《Chinese Journal of Polymer Science》2004年第4期321-325,共5页高分子科学（英文版）

基　　金：This work was supported by the National Natural Science Foundation of China (Project No. 29974016).

摘　　要：Poly(methyltetraphenylphenylsilylene-co-bis(methylphenylsilyl)acetylene) (PSA) was synthesized by the cocondensation reaction of methyltetraphenylphenyldichlorosilane and bis(chloromethylphenylsilyl)acetylene with sodium in toluene. The PSA thus obtained was soluble in most organic solvents, and its molecular weight was smaller than that of poly[(disilanylene)acetylenes] with alkyl- or aryl-substitution because of the great steric congestion of tetraphenylphenyl groups. The optical and electronic properties of the polymer were investigated. The results show that PSA has strong UV absorption and fluorescence emission, the maximum UV absorption wavelength of PSA is 330 nm, which shows a considerable red-shift in comparison with that of poly(methylphenylsilylene-co-methylphenylsilylacetylene) (PSI) and alkyl- substituted poly[(disilanylene)acetylenes]. A strong photoluminescence band at 470 nm in THF and 432 nm in benzene can be observed in the visible region, respectively. Treatment of the films of PSA with I 2 vapor afforded conducting films. The conductivity of PSA thin film doped with I 2 was measured to be 0.35 S cm -1 in the air which is lower than that of poly(methyltetraphenylphenylsilylene-co-bis(methylphenylsilyl)phenylene), but higher than that of σ-π polymers without tetraphenylphenyl groups. As an explanation, the tetraphenylphenyl group is a large π-electron-conjugated group; after being introduced to the Si atoms of the polysilanes, the interaction between π-electrons of the tetraphenylphenyl groups and the σ- electrons conjugated along the Si—Si bonds is increased strongly, and the σ-electrons can be conjugated more extensively along the main chain of the polysilanes.Poly(methyltetraphenylphenylsilylene-co-bis(methylphenylsilyl)acetylene) (PSA) was synthesized by the cocondensation reaction of methyltetraphenylphenyldichlorosilane and bis(chloromethylphenylsilyl)acetylene with sodium in toluene. The PSA thus obtained was soluble in most organic solvents, and its molecular weight was smaller than that of poly[(disilanylene)acetylenes] with alkyl- or aryl-substitution because of the great steric congestion of tetraphenylphenyl groups. The optical and electronic properties of the polymer were investigated. The results show that PSA has strong UV absorption and fluorescence emission, the maximum UV absorption wavelength of PSA is 330 nm, which shows a considerable red-shift in comparison with that of poly(methylphenylsilylene-co-methylphenylsilylacetylene) (PSI) and alkyl- substituted poly[(disilanylene)acetylenes]. A strong photoluminescence band at 470 nm in THF and 432 nm in benzene can be observed in the visible region, respectively. Treatment of the films of PSA with I 2 vapor afforded conducting films. The conductivity of PSA thin film doped with I 2 was measured to be 0.35 S cm -1 in the air which is lower than that of poly(methyltetraphenylphenylsilylene-co-bis(methylphenylsilyl)phenylene), but higher than that of σ-π polymers without tetraphenylphenyl groups. As an explanation, the tetraphenylphenyl group is a large π-electron-conjugated group; after being introduced to the Si atoms of the polysilanes, the interaction between π-electrons of the tetraphenylphenyl groups and the σ- electrons conjugated along the Si—Si bonds is increased strongly, and the σ-electrons can be conjugated more extensively along the main chain of the polysilanes.

关 键 词：POLYSILANE SYNTHESIS Tetraphenylphenyl group Optical-electronic properties 

分 类 号：O631[理学—高分子化学]