基于非共价键作用的瓜环—柱芳烃超分子组装体的构筑及其性能研究

It is well known that the cucurbit[n]urils (Q[n]s) and pillar[n]arenes (P[n]s) have achieved rapid development in their respective fields, whereas the researches of cucurbit[n]urils-containing pillar[n]arenes is still in its infancy. In this project, we will select, design and synthesise cucurbit[n]urilsand pillar[n]arenes with proper structure features as building blocks, construct of a series of supramolecular self-assmblies of cucurbit[n]uril-pillar[n]arene based on intermolecular non-covalent bond of cucurbit[n]uril and Pillar[n]arene and investigate the formation mechanism, which are our main aim and key scientific point. This project mainly includes the construction and characterization of two kinds of cucurbit[n]uril-pillar[n]arene systems: the first category is the cucurbit[n]uril-pillar[n]arene supramolecular assembly, the second category is the cucurbit[n]uril-pillar[n]arene-guest supramolecular assembly. On the basis of this study, the functional properties were studied. For the first type of system, the functional properties such as adsorption, separation and enrichment were studied; For the second type of system, the main research on its optical, electrical and chiral recognition and other functional properties. At last, a new research area could be established in the cucurbit[n]url chemistry or pillar[n]arene chemistry.

瓜环以及柱芳烃在各自的领域中都取得了飞速的发展，但同时融合瓜环以及柱芳烃这两种大环化合物的研究工作尚处于萌芽状态。本项目以瓜环和柱芳烃为构筑模块，设计、合成特定结构的瓜环和柱芳烃，选择结构、性质匹配的瓜环—柱芳烃组合，通过分子间的非共价键作用构筑结构新颖、性质特异的超分子组装体，探究构筑机制，达到能动设计、调节和控制合成新型超分子组装体的目的。本项目主要包括两大类瓜环—柱芳烃组装体的构筑及表征：第一类为瓜环—柱芳烃自身超分子组装体，第二类为瓜环—柱芳烃—客体分子超分子组装体，并在此基础上，对其功能性质进行研究：对于第一类组装体，主要研究其吸附、分离、富集等功能性质；对于第二类组装体，主要研究其光学、电学、分子运动以及手性识别等方面的功能性质，以此发展和促进形成瓜环化学或柱芳烃化学中一个新的研究方向。

本项目以瓜环和柱芳烃为构筑模块，设计、合成了系列不同聚合度的瓜环以及特定结构柱芳烃：甲基柱芳烃、吡啶柱芳烃、对氨基吡啶柱芳烃、萘乙烯吡啶柱芳烃、对苯撑乙烯柱芳烃等，并合成了系列具有不同功能基团的客体分子。重点研究了不同瓜环、柱芳烃与客体分子的作用特征、作用位点、作用力、热力学及动力学性质等，探讨溶液种类、体系酸碱度、竞争或协同客体分子对瓜环—柱芳烃超分子体系的影响，系统评估不同类型的客体分子与各种瓜环—柱芳烃形成超分子组装体的结构特征，为这类复合型主客体组装体的应用提供理论依据。通过项目研究，以非共价键作用构筑的瓜环—柱芳烃超分子组装体，将两个相对独立的大环化合物化学联系起来，使瓜环与柱芳烃优良的分子性能结合在一起, 达到 1＋1＞2的效果，发展和促进形成瓜环化学或柱芳烃化学中一个新的研究方向。