近红外电致变色胆甾相液晶高分子的设计、合成及旋光开关性质  

Synthesis and characterization of novel near-infrared electrochromic cholesteric liquid crystalline polymers with chiroptical switching properties

作　　者：陈丰坤[1] 张洁[1] 宛新华[1] 

机构地区：[1]高分子化学与物理教育部重点实验室北京分子科学国家实验室北京大学化学与分子工程学院,北京100871

出　　处：《中国科学：化学》2011年第2期341-350,共10页SCIENTIA SINICA Chimica

基　　金：国家自然科学基金(20834001)的资助

摘　　要：通过单体4′-甲氧基苯基-4-烯丙氧基苯甲酸酯(M1)、(S)-(-)-N-(5-己烯基)-6-(4′-(2-甲基丁氧基)苯基)-蒽醌-2,3-二羧酸酰亚胺(M2)与聚甲基氢硅氧烷间的硅氢加成反应,制得了3个新的具有近红外电致变色性质的侧链型液晶共聚物(PC5A10,PC5A20CB,PC5A30CB),并对其液晶性,电化学,光谱电化学和旋光开关性质进行了表征.当M2单体的含量为10mol%,20mol%时,共聚物可形成胆甾相液晶,而当其含量为30mol%时,所能形成的液晶相为近晶A相.3个共聚物的循环伏安曲线均出现了两对可逆的氧化还原峰,分别对应于蒽醌酰亚胺基团得电子而形成自由基阴离子和二价阴离子.中性态时,共聚物在420nm处有较强吸收,而当被还原为自由基阴离子后,在近红外区域840nm出现了新的强烈的吸收.以聚合物为阴极电致变色层,普鲁士蓝为离子储存层的全固态电致变色器件在800nm有较好的光学调制性.此外,本文还就该器件的电化学调控手性光开关性质进行了初步研究.The side-chain liquid crystalline copolymers（PC5A10,PC5A20CB,PC5A30CB） bearing near-infrared electrochromic chromophores were synthesized by hydrosilylation reactions between 4＇-methoxyphenyl 4-（allyloxy）benzoate（M1）,（S）-（-）-N-（hex-6-enyl）-6-（4＇-（2-methylbutoxy）phenyl）-anthraquinone-2,3-dicarboxylic imide（M2） and poly（methylhydrosiloxane）.The thermotropic liquid crystalline properties,redox activities,and spectroelectrochemical behaviors of these polymers were characterized.The copolymers containing 10 mol% and 20 mol% M2 exibited cholesteric liquid crystalline phases,whereas the polymer with 30 mol% of M2 formed a smectic A phase.Two reversible redox peaks appeared in the cyclic voltammograms of the copolymers,corresponding to the radical anions and the dianions after two successive one-electron reductions,respectively.In the neutral state,the copolymers showed absorption peaked at 420 nm,while a new strong absorption peaked at 840 nm appeared when reduced to radical anions.Optical modulation at 800 nm was carried out in an all-solid state electrochromic device consisting of the copolymers as the cathodic electrochiromic layer and an additional layer of Prussian blue as the ion storage layer.Furthermore,the redox triggered chiroptical switching property of this device was discussed.

关 键 词：胆甾相液晶 近红外电致变色 旋光开关 侧链型液晶高分子 

分 类 号：O753.2[理学—晶体学]