多环与笼状分子主体的构筑及功能化

The fabrication of high level supramolecular assembly based on multiple macrocyclic hosts is a hot research topic in the field of supramolecular chemistry. This project will use pillar[5]arenes as building blocks and contain the following five aspects: (1) Multiple macrocyclic hosts are designed and synthesized through SNAr reactions, and their gas absorption properties will be investigated. (2) The host-guest interactions between these multiple macrocyclic hosts and proper guests are studied, based on which the [3]rotaxane to [7]rotaxane will be synthesized. (3) Two interaction sites will be invited in the axle molecules, through addition of environment stimuli (such as solvents and temperature), multiple macrocycles will shuttling over the axle simultaneously. (4) By derivatizing the rigid pillar[5]arene dimer, innermolecular catenane will be fabricated. (5) Based on host-guest interactions between multiple macrocyclic hosts and proper guest and the metal coordinations, dynamic catenanes will be constructed. This project will improve the application of pillararenes in the construction of complicated high-level supramolecular assemblies and give a new idea for exploring novel molecular devices.

基于多环主体构筑高级超分子组装体是一项非常重要且有待进一步发展的研究方向。本申请课题以柱[5]芳烃为基本结构单元，(1)通过芳香亲核取代反应，拟制备多环状主体化合物，研究其气体吸附等功能；(2)以多环或笼状分子出发，研究其主客体络合作用，构筑寡聚轮烷[3]轮烷‒[7]轮烷；(3)在轮烷中引入两个主客体作用位点，通过环境刺激（如溶剂、温度等）实现多个大环在哑铃状轴线分子上的同步穿梭运动，制造分子器件；(4)以柱[5]芳烃二聚体出发，通过硝基还原等反应进一步衍生化，制备内索烃结构；(5)利用柱[5]芳烃的主客体作用和金属铂的配位作用，组装构筑动态索烃结构。本申请课题的成功实施，将实现复杂高级互锁结构寡聚轮烷和内索烃等的构筑，为制备新型分子器件提供新的思路和平台。

本申请课题以柱[5]芳烃为基本结构单元，进行拓展和衍生化，设计制备多环和笼状分子主体：(1)通过芳香亲核取代反应，制备了一系列氧杂杯[4]芳烃桥连的柱[5]芳烃二聚体，研究了其平面手性和异构现象；(2)以柱[5]芳烃二聚体出发，研究其主客体络合作用，构筑了一系列具有平面手性的[2]轮烷和[3]轮烷；(3)以四苯乙烯为链接单元，构筑了笼状柱[5]芳烃四聚体，同时制备了柱[5]芳烃苯并菲四聚体，研究了其与2,4,7-三硝基芴酮的主客体性质；(4)制备了环氧化柱[5]芳烃醌类衍生物。本项目实现了复杂手性互锁结构轮烷的构筑，引入了超分子手性的新议题，为制备手性分子器件提供新的思路和平台。