偶氮苯光色基元修饰的杯芳烃的荧光性能和液晶行为  

Fluorescence Property and Liquid Crystalline Behavior of Calix[4]arene Containing Azobenzene Photochromic Group

作　　者：龚林波[1] 龚淑玲[1] 董海青[1] 张春雷[1] 陈远荫[1] 

机构地区：[1]武汉大学化学与分子科学学院,武汉430072

出　　处：《应用化学》2006年第9期1023-1026,共4页Chinese Journal of Applied Chemistry

摘　　要：对甲基偶氮苯酚1与1，6-二溴己烷反应合成4．甲基-4’-（ω-溴己氧基）偶氮苯2，化合物2与杯[4]芳烃作用得到下缘有偶氮苯光色基元修饰的杯[4]芳烃3，用。HNMR和ESI—MS验证了化合物3的结构。荧光光谱分析表明，在生色团浓度为8．0×10^-6～8．0×10^-4mol／L的范围内，化合物3的荧光强度比化合物1、2高2～4倍，说明偶氮苯基元键连到杯芳烃骨架上后，其荧光量子产率可以明显提高。用热台显微镜和DSC分析了化合物的液晶行为。化合物2降温过程中在87．4～84．2℃呈现液晶性，而化合物3在升温过程中，于209．4～219．5℃形成镶嵌织态。杯芳烃骨架有利于偶氮苯液晶单元构象的固定以及高温液晶相的形成。The reaction of 4′-hydroxy-4-methyl azobenzene （ 1 ） and 1,6-dibromohexane afforded 6-bromo-1 - （ （4-（（4-methylphenyl） azo） phenyl） oxy ） hexane （ 2 ）, which was further reacted with p-tert-butylcalix [ 4 ] arene to give calix [ 4 ] arene derivative（3）, whose lower rim was modified by azobenzene photochromic group. The structure of compound 3 was characterized by ^1H NMR and ESI-MS. The fluorescence intensity of compound 3 is 2 -4 times higher than that of compounds I and 2 as the azobenzene group concentration was in the range of 8.0 × 10^-5 to 8.0 ×10^-4 mol/L, indicating that the fluorescence quantum yield of azobenzene group can be improved by attaching it to the calix [ 4 ] arene skeleton. The liquid crystalline behavior of compound 3 was studied by POM and DSC. Compound 3 exhibited enhanced texture of smectic liquid crystal from 209.4 ℃ to 219.5℃ on heating, while compound 2 exhibited liquid crystalline phase from 87.4 to 84. 2℃ on cooling. It was found that the calix[4] arene skeleton can fix the conformation of the azobenzene photochromic group and help the formation of liquid crystalline morphology.

关 键 词：偶氮苯 杯[4]芳烃 热致液晶 荧光 

分 类 号：O621.2[理学—有机化学]