假1,2-二苯乙烯型偶氮苯合成、表征及其光致异构性能

doi:10.11944/j.issn.1000-0518.2016.04.150282

摘要/Abstract

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^-1~10⁰ s^-1,反→顺异构转变速率常数k_t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k_t影响比二溴代物大,空间位阻效应对二溴代物的k_t影响比单溴代物大,顺→反异构转变速率常数k_c与k_t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。

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

Abstract:

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^-1 to 10⁰ s^-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.

Key words: pseudostilbene azobenzenes, azo coupling, photochromic, cis/trans isomerization, rate constant

宋秀美, 冯宗财, 汪朝阳, 陈小玲, 梁志美, 梁燕玉. 假1,2-二苯乙烯型偶氮苯合成、表征及其光致异构性能[J]. 应用化学, 2016, 33(4): 442-451.

SONG Xiumei, FENG Zongcai, WANG Zhaoyang, CHEN Xiaoling, LIANG Zhimei, LIANG Yanyu. Synthesis, Characterization and Photoisomerization Properties of Pseudostilbene Azobenzenes[J]. Chinese Journal of Applied Chemistry, 2016, 33(4): 442-451.

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