Supramolecular Polymerization in Liquid Crystalline Media: Toward Modular Synthesis of Multifunctional Core?Shell Columnar Liquid Crystals
Supramolecular Polymerization in Liquid Crystalline Media: Toward Modular Synthesis of Multifunctional Core?Shell Columnar Liquid Crystals
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液晶介质中的超分子聚合：多功能核壳柱状液晶的模块化合成
DOI：
10.1021/jacs.9b03961
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发表时间：
2019
影响因子：
15
通讯作者：
Aida Takuzo
中科院分区：
文献类型：
--
作者：
Yano Keiichi;Hanebuchi Takahiro;Zhang Xu-Jie;Itoh Yoshimitsu;Uchida Yoshiaki;Sato Takuro;Matsuura Keisuke;Kagawa Fumitaka;Araoka Fumito;Aida Takuzo
最近，我们发现了一个模块化的合成方法，通过超分子聚合在液晶介质中构建核壳柱状液晶（LC）。在目前的工作中，我们成功地证实了我们的模块化合成方法有可能被广泛扩展到多功能柱状LC的开发。本文以手性苯三甲酰胺衍生物2，2，6，6-四甲基哌啶-1-氧基为端基，在4-氰基-4 ′-戊氧基联苯（5 OCB）的超分子聚合反应体系中，首次构建了具有电场和磁场双重定向性的核壳柱状液晶，其已知通过三重氢键阵列形成螺旋超分子聚合物。NO3-NH * 单独形成氢键液相而没有任何长程结构有序。然而，当5 OCB与NO3-NH * 以1：3的摩尔比混合时，5 OCB的非晶液晶介质经历“结构有序增加”的中间相转变，在113至51 °C的温度范围内提供具有六边形排列的核-壳柱状几何形状的光学活性单一液晶相。前所未有的是，这种核-壳柱状LC可以使其柱在电和磁两方面取向，从而导致单向柱状有序。
Recently, we discovered a modular synthetic approach for constructing core–shell columnar liquid crystals (LCs) by supramolecular polymerization in LC media. In the present work, we successfully confirmed that our modular synthetic approach has the potential to be widely extended to the development of multifunctional columnar LCs. Herein, we constructed the first core–shell columnar LC that was proved to be orientable by both electric and magnetic fields by the supramolecular polymerization ofNODiskNH*in a nematic LC medium of 4-cyano-4′-pentyloxybiphenyl (5OCB).NODiskNH*is a chiral benzenetricarboxamide derivative bearing 2,2,6,6-tetramethylpiperidine 1-oxyl termini, which is known to form a helical supramolecular polymer via a triple hydrogen-bonding array.NODiskNH*alone formed a hydrogen-bonded liquid phase without any long-range structural ordering. However, a nematic LC medium of 5OCB, when mixed withNODiskNH*at a molar ratio of 1:3, underwent a “structural order-increasing” mesophase transition, affording an optically active single LC phase with a hexagonally arranged core–shell columnar geometry in a temperature range from 113 to 51 °C. Unprecedentedly, this core–shell columnar LC can orient its columns both electrically and magnetically, resulting in unidirectional columnar ordering.