以外壁作用为主导的瓜环-杯芳烃超分子自组装及其功能性质

It is well known that the Q[n]-based host-guest chemistry and coordination chemistry are two main research areas in the Q[n]-chemistry, whereas the functions of the electropositive outer surface of Q[n] is rarely known. In this project, based on factor of the selctive interaction of outer surface of Q[n] for the aromatic ring, we will select, design and synthesise cucurbit[n]urils and calix[m]arences with proper structure features as building blocks, construct of a series of supramolecular self-assmblies of cucurbit[n]uril-calix[m]arence hybrids based on the outer-surface interaction of Q[n] and investigate the formation machanism, which are our main aim and key scientific point. The main content in the project includes: the construction and characteristics of supramolecular self-assmblies of normal cucurbit[n]urils and calix[m]arences systems; alkyl-substituted cucurbit[n]urils and calix[m]arences systems; hemicucurbit[n]urils and calix[m]arences. Based on the invastigations of the cucurbit[n]uril-calix[m]arence-based supramolecular self-assmblies, the functional properties, including basic properties of themsevles, absorption for gases or volatile compounds, seperation as a fix phase materials, and enrichment of certain materials. At last, a new research area could be established in the cucurbit[n]url chemistry or calix[m]arence chemistry.

瓜环化学中主客体化学及配位化学已为人熟知；但基于瓜环正电性外壁作用的化学还未受到足够重视。本项目根据瓜环正电性外壁对含芳环有机分子选择性作用的特点，以瓜环和杯芳烃为构筑模块，设计、合成特定结构的瓜环和杯芳烃；选择结构、性质匹配的瓜环-杯芳烃组合，通过瓜环的外壁作用构筑结构新颖、性质特异的超分子自组装体，探究构筑机制，达到能动设计、调节和控制合成，是本项目的核心内容，也是本项目的研究目标和拟解决的关键科学问题。包括：普通瓜环-杯芳烃超分子自组装体的构筑及表征；取代基在特定位置上的瓜环与杯芳烃的超分子自组装体的构筑及表征；非水溶剂中半瓜环与杯芳烃的超分子自组装体的构筑及表征。在此基础上，研究瓜环-杯芳烃超分子自组装体功能性质，包括：瓜环-杯芳烃超分子自组装体基本性质；吸附；分离；富集等功能性质。发展和促进形成瓜环化学或杯芳烃化学中的一个新的研究方向。

本项目利用瓜环的空腔作用及外壁作用，设计并构筑了结构新颖、性质特异的瓜环-杯芳烃超分子自组装体系，并对瓜环-杯芳烃超分子自组装体系的性质进行研究。杯[4]芳烃的取代基可进入八元瓜环的空腔形成超分子自组装体系，当引入有机小分子后，可使体系的荧光增强或猝灭，从而可作为检测这些化合物的荧光探针。利用瓜环的外壁作用，设计并构筑了具有多孔和可吸附性能的瓜环-杯芳烃基超分子有机框架材料，如六元瓜环-磺化杯[4,6]芳烃超分子框架材料可制作成红色荧光材料并作为甲醛和吡啶气体的指示剂；七元瓜环与磺化杯[4]芳烃超分子自组装体系可以有选择性地吸附某些有机染料产生多种荧光发射，用来制备固体荧光材料；八元瓜环-4-磺酰杯[6]芳烃超分子框架材料可用于离子选择性吸附。瓜环-杯芳烃超分子有机框架材料可在固体荧光材料、海水淡化、离子富集、放射性离子污染源处理及水软化等方面有潜在应用。另外，通过[2+2]光二聚，将非共价超分子(C[4]SP•Q[8])转化为共价键的大环结构((C[4]SP•Q[8])4)，极大促进了复杂超分子体系的构建过程。