基于瓜环外壁作用的瓜环超分子配位聚合物的合成及其功能研究

In this project, we will design and synthesise a series of supramolecular polymers based on direct coordination of metal ions to the cucurbit[n]urils by using an induced strategy, in which the back-interaction of cucurbit[n]urils are the driving forces. Based on the chacaterastics of the back-interaction of cucurbit[n]uirls in the costruction of the supramolecular coordination polymers, the back-intractions include 1) electrodonating effect of the alkyl-substituted groups on the back of cucurbit[n]urils; 2) ∙∙∙ stacking between portal carbonyl groups of cucurbit[n]uril as well as C–H∙∙∙ interaction between methine or methylene moieties on the back of cucurbit[n]urils and aromatic moiety of organic structure inducers; 3) unusual hydrogen bonding between methine or methylene moieties on the back of cucurbit[n]urils as well as ion-dipole interactions between positive portal carbonyl carbon of cucurbit[n]urils and chloride anion from polychlorometallate anions; 4) coordination interaction between hydroxyl groups on the back of cucurbit[n]urils with metal ions. Studies on the functions of these cucurbit[n]urils-based supramolecular coordination polymers. Using the back-interaction of cucurbit[n]urils strategy, one can not only constructe of novel poly-dimensional and polycomponents cucurbit[n]urils-based supramolecular coordination polymers, but also find new methods, new technologies and regular patterns to construct such supramolecular self-assemblies. Based on the characterestic of the supramolecular coordination polymers, these systems could be used in the fields, such as nano-technology, molecular machine, sensers and actuators, catalyst, energy storage technology and so on.

本项目拟利用瓜环外壁作用诱导的策略，设计并合成瓜环-金属超分子配位聚合物。根据瓜环外壁作用类型，研究内容包括：i) 利用瓜环外壁上取代烷基的推电子作用合成瓜环―金属超分子配位聚合物；ii) 利用有机导向剂中芳环与瓜环外壁作用合成瓜环―金属超分子配位聚合物；iii) 利用无机阴离子导向剂与瓜环外壁作用合成瓜环―金属超分子配位聚合物；iv) 利用瓜环外壁上羟基的配位作用合成瓜环―金属超分子配位聚合物。对所得超分子配位聚合物在吸附、分离、识别等功能性质的研究。通过对建立在瓜环外壁作用基础上的瓜环配位聚合物的合成及其功能研究，分别探究各瓜环外壁作用对瓜环―金属超分子配位聚合物合成促进作用机制，同时还需探究不同瓜环外壁作用共同对瓜环―金属超分子配位聚合物合成促进或抑制作用的机制，从而达到能动地设计、控制合成具有结构新颖、特定功能性质瓜环基超分子配位聚合物，发展和建立瓜环配位化学中一个新的研究方向。

本项目利用瓜环外壁作用和端口配位作用，设计并构筑了结构新颖、性质特异的瓜环基超分子自组装体系，并对瓜环基超分子自组装体系的性质进行研究。利用瓜环外壁作用，设计并构筑了具有多孔和可吸附性能的瓜环基超分子有机框架材料，负载各种荧光染料后获得固体荧光材料，并将其用于挥发性有机物化合物的识别检测，如六甲基六元瓜环超分子框架材料制作的荧光材料可作为二乙醚、四氯甲烷、甲醇和乙醇气体的指示剂；十元瓜环超分子框架制作的荧光材料可作为吡啶、苯、乙醇和四氢呋喃气体的指示剂；四甲基六元瓜超分子框架材料制作的荧光材料可作为乙醇、三氯甲烷和甲醇的气体指示剂。四甲基六元瓜环、八元瓜环构筑的超分子有机框架可用于贵金属离子Pd、Au选择性捕集，十二甲基六元瓜环构筑的超分子框架可用于苯二胺异构体的分离。此外，单羟基七元瓜环和十二羟基六元瓜环构筑的超分子框架材料可分别用于甲醇和多氯甲烷的吸附。瓜环基超分子有机框架材料可在固体荧光材料、异构体分离、有害气体吸附、金属离子富集与分离，以及酯化催化与染料降解等方面有潜在应用。