假1,2-二苯乙烯型偶氮苯合成、表征及其光致异构性能  

Synthesis,Characterization and Photoisomerization Properties of Pseudostilbene Azobenzenes

作　　者：宋秀美 冯宗财 汪朝阳[3] 陈小玲 梁志美 梁燕玉 

机构地区：[1]岭南师范学院产业技术研究院,广东高校新材料工程技术开发中心,广东湛江524048 [2]岭南师范学院化学化工学院,广东湛江524048 [3]华南师范大学化学与环境学院,广州510006

出　　处：《应用化学》2016年第4期442-451,共10页Chinese Journal of Applied Chemistry

基　　金：广东省自然科学基金资助项目(S2011010001544,2014A030313429);湛江市科技攻关计划项目(2014B011031,2015A02008)

摘　　要：合成系列假1,2-二苯乙烯型偶氮苯,利用FT-IR、NMR、ESI-MS和元素分析等技术手段确定目标化合物结构,并通过UV-Vis光谱研究其光致变色性能,测定其溶液态光致顺反异构速率常数,同时考察其在聚甲基丙烯酸甲酯掺杂薄膜中抗疲劳性能,结果表明,目标化合物在乙酸乙酯中π-π^＊能级低于n-π^＊能级,且两个能级出现重叠,异构转变速率常数数量级10^-1-10^0s^-1,反→顺异构转变速率常数kt受到偶极-偶极作用力和空间位阻效应影响,偶极-偶极作用力对单溴代物的kt影响比二溴代物大,空间位阻效应对二溴代物的kt影响比单溴代物大,顺→反异构转变速率常数kc与kt大小顺序相反,在聚甲基丙烯酸甲酯掺杂薄膜中有良好的抗疲劳性能。A series of novel pseudostilbene azobenzenes was synthesized and their structures were characterized by FT-IR,NMR,MS（ ESI） and elemental analysis. The photoisomerization properties and reversible cis / trans isomerization rate constants in solvent were measured via UV-Vis spectroscopy,as well as the fatigue resistance property in polymethyl methacrylate（ PMMA） film was performed. The azobenzenes in ethyl acetate have the two bands of π-π^＊and n-π^＊inverted on the energy scale and π-π^＊and n-π^＊bands are practically superimposed. The isomerization rate constants range from 10^- 1to 10^0s^- 1. The trans to cis isomerization rate constants depend on the dipole-dipole interactions and molecular steric hindrance,with the dipole-dipole interactions having larger impact on monobromo-azobenzenes than dibromo-azobenzenes,and a reverse impact from molecular steric hindrances. The faster trans to cis transformation corresponds to the slower cis to trans transformation. The azobenzene has a good fatigue resistance to some extent in PMMA film.

关 键 词：假二苯乙烯型偶氮苯 重氮偶合 光致变色 顺反异构 速率常数 

分 类 号：O625.6[理学—有机化学]