基于三氮唑修饰的苯并菲衍生物的超分子手性凝胶  

Supramolecular Chiral Gel Based on Triazole-Modified Triphenylene Derivative

作　　者：张红莉 程军杰 邹纲[1] ZHANG Hongli;CHENG Junjie;ZOU Gang(Department of Polymer Science and Engineering,University of Science and Technology of China,Hefei 230026,China)

机构地区：[1]中国科学技术大学高分子科学与工程系

出　　处：《功能高分子学报》2019年第6期728-734,共7页Journal of Functional Polymers

基　　金：国家自然科学基金(21574120)

摘　　要：通过叠氮-炔Click反应和酯化反应,合成了3种以长烷基链为臂、苯并菲为核的盘状衍生物。采用核磁共振、紫外吸收对该产物的分子结构进行了表征。讨论了溶剂极性、连接基元类型、柔性链链长等因素对苯并菲衍生物形成超分子凝胶的影响。研究表明:低极性溶剂有利于促进苯并菲衍生物形成超分子凝胶;三氮唑修饰的苯并菲衍生物形成的超分子凝胶更稳定;在三氮唑修饰的苯并菲衍生物自组装过程中引入(+)或(–)柠檬烯为手性溶剂,可成功诱导非手性苯并菲盘状衍生物形成特定光学活性的超分子手性凝胶,真空干燥除去柠檬烯后,苯并菲衍生物凝胶仍具有宏观光学活性,表现出优异的手性记忆效应。Supramolecular gels are formed by the self-assembly of small organic molecules of which the self-assembled nanostructures are entangled to form a 3 D network. During the self-assembly, gelator-solvent interactions are able to subtly regulate these interactions and play an important role during the gel formation. In this paper, we synthesized several triphenylene derivatives and lucubrated the necessary conditions for gel formation by adjusting the molecular structures of the triphenylene derivatives and the polarity of the organic solvent. Low polarity of organic solvent is favorable for supramolecular assembly. Furthermore, the triazole-modified triphenylene derivatives are easier to form a gel by selfassembling in non-polar solvent, but longer flexible chains result in unstable gels. Besides, another triphenylene derivative that the flexible chain is linked by an ester bond cannot form supramolecular gel. It indicates that the dipole-dipole and π-πinteractions between 1,2,3-triazoles play a synergic effect on gel formation, which stabilize the columnar assembly of triphenylene moiety. Furthermore, shorter flexible chain can increase the stability of the resulting supramolecular gel. On this basis,(+)-or(-)-limonene is introduced as a chiral solvent during the self-assembly process of triazole-modified triphenylene derivative. As a result, a specific optically active supramolecular chiral gel is formed successfully, and the optically activity of the supramolecular assembly is maintained after removing limonene.

关 键 词：苯并菲 超分子组装 有机凝胶 手性 

分 类 号：O631.2[理学—高分子化学]