含蒽醌酰亚胺基元的旋光性聚乙炔及其近红外性质

用改进的方法合成了6-溴蒽醌-2,3-二羧酸酐,制备出一个新的非手性炔类单体——N'-(1-己基庚基)-6-乙炔基蒽醌-2,3-二羧酸酰亚胺,并在铑配合物的催化下得到相应的聚合物.当在催化体系中加入手性1-苯基乙胺时,所得的聚合物具有旋光活性,在紫外吸收区具有明显的Cotton效应.聚合物保持了蒽醌酰亚胺基元的近红外电致变色性质,对其施加-0.6 V的电压后,在500～1200 nm波长范围出现了明显的吸收谱带,最大吸收波长为820 nm.

A NOVEL CHIRAL POLYACETYLENE CONTAINING ANTHRAQUINONE IMIDE AND ITS NEAR-INFRARED PROPERTIES

Synthesis and near-infrared electrochromic properties of a novel chiral polyacetylene containing anthraquinone imide as the pendant group are reported.The monomer precursor,6-bromoanthraquinone-2,3-dicarboxylic anhydride,has been synthesized in a good yield via an improved synthetic route.The monomer N′-(1-hexylheptyl)-6-ethynylanthraquinone-2,3-dicarboxylic imide was converted to the polymer by the catalysis of chloronorbornadiene rhodium(Ⅰ) dimer.Chiral polymers based on achiral monomers could be achieved by using chiral(R)/(S)-phenylethylamine as the cocatalyst,which have obvious Cotton effects in the ultraviolet-visible region.Properties of polymers,such as chirality and solubility could be modulated easily by changing the imide group.The novel polymers have electrochromic properties similar to those of the small anthraquinone imide molecule.Intense absorption peaked at 820 nm in the visible-near infrared range of 500-1200 nm has been observed in the single electron reduction state.