3’,5’-二溴-2,4-二羟基偶氮苯的合成、晶体结构和光致异构性能（英文）  

Synthesis,Crystal Structure and Photoisomerization Property of 3',5'-Dibromo-2,4-dihydroxylazobenzene

作　　者：宋秀美[1,2] 冯宗财[1] 汪朝阳[2] 王跃川[3] 麦乐容 

机构地区：[1]湛江师范学院化学科学与技术学院广东高校新材料工程技术开发中心,湛江524048 [2]华南师范大学化学与环境学院,广州510006 [3]四川大学高分子材料工程国家重点实验室,成都610065

出　　处：《化学通报》2014年第8期784-789,共6页Chemistry

基　　金：广东省自然科学基金项目(52011010001544);广东省高校第3期人才特别基金项目(广财教[2011]431);高分子材料工程国家重点实验室开放基金项目(KF201208)资助

摘　　要：以对硝基苯胺为原料,通过溴代、去氨基、硝基还原和重氮耦合反应合成了3’,5’-二溴-2,4-二羟基偶氮苯,利用FT-IR,1H NMR,13C NMR,MS,元素分析和X射线单晶衍射等方法对标题化合物的结构进行了表征。X射线单晶衍射结果表明,该晶体属于单斜晶系,P1 21/c1空间群,晶胞参数为:a=2.0107(3)nm,b=0.42111(7)nm,c=0.16175(3)nm,β=94.408(2)°,V=1.3655(4)nm3,Z=4,Dc=1.897 g/cm3,μ=5.941 mm-1,F(000)=760,R1=0.0762,wR2=0.2127[I>2σ(I)],标题偶氮苯分子以E型异构体存在。其光致异构性能研究表明,在紫外光的照射下,标题分子可实现E-Z异构转化,其稀溶液E-Z光致异构转化遵循一级动力学方程ln[(A0-Aeq)/(At-Aeq)]=kt×t。Starting from p-nitroaniline, the titled compound, 3 ＇ ,5 ＇ -dibromo-2,4-dihydroxylazobenzene was obtained via sequential reactions of dibromination, deamination, nitro-reduction and diazo coupling. The chemical structure and absolute configuration of the titled compound were confirmed by FT-IR, 1H NMR, t3C NMR, MS, elemental analysis, especially by the X-ray single crystal diffraction. The crystal crystallizes in monoclinic space group P1 21/el, with a = 2. 0107 （3） nm, b = 0.42111（7） nm, c=0.16175（3） nm, β=94.408（2）°, V=1.3655（4） nm3, Z=4, Dc =1.897 g/cm3, μ=5.941 mm-1, F（000） = 760, R1 = 0. 0762 and wR2=0. 2127, S = 1. 033. X-ray analysis indicates that the titled compound exists as E-isomer azobenzene. The photoisomerization behavior investigated by UV-Vis spectrum reveals that the titled compound was capable of undergoing efficient E-Z photoisomerization. And there was a kinetic advantage of azobenzene E-Z photoisomerization in its diluted solution according to the first-order reaction equation In[ （A0 -Aeq ）/（At -Aeq ） ] = k1 × t.

关 键 词：3' 5' -二溴-2 4-二羟基偶氮苯 光致异构 Z-E异构 晶体结构 

分 类 号：O625.6[理学—有机化学]