高效高选择性的动态超分子纳米容器绿色催化剂的开发

The design of new catalysts with high efficiency and selectivity has served as the key research in modern chemistry. In recent decades, growing attention has been attracted to the search for innovative and highly selective biomimetic catalytic systems outside the traditional homogeneous and heterogeneous catalytic process. This project plans to use the self-assembled supramolecular nano-vessel system to solve the problems of conventional transition metal catalysts, such as poor water-solubility, poor stability and poor selectivity. The project will start from the design of water-soluble, stimuli-responsive chiral supramolecular nano-vessels to serve as the nano-reactor. Driven by hydrophobic effect and electrostatic interactions, specific transition-metal catalysts will be encapsulated into the nano-vessel, which will transfer the traditional organic phase reaction into the aqueous phase. This strategy will increase the stability of the original catalysts by preventing their aggregation or poisoning. The confinement effect given by the nano-vessel is expected to facilitate extra size-, chemo- and stereo-selectivity; the pre-organization effect will increase the local concentration of the reactants and manipulate their conformation toward the transition-state to accelerate the reaction. The ultimate goal of this project is to establish a novel supramolecular green catalysis system based on the stimuli-responsible self-assembled nano-vessels and their host-guest chemistry.

高效高选择性的新型催化剂设计合成一直都是现代化学的研究重点。近几十年中人们开始在传统的均相催化与非均相催化体系之外寻找新颖的仿生催化体系。本项目"高效高选择性的动态超分子纳米容器绿色催化剂的开发"计划利用自组装的金属配位超分子体系来解决传统过渡金属催化剂在水溶性，稳定性及选择性等方面的问题。首先设计结构精确、具有刺激响应性的水溶性手性超分子容器作为有机反应的纳米反应器。在疏水作用或正负电荷相互作用下将常规金属有机催化剂担载在纳米容器的手性空腔当中以转移有机相反应到水相中进行。纳米容器的限域效应预期可以提高催化反应的尺寸选择性，同时增加底物的有效浓度并控制其构型接近反应的过渡态，进而加速反应进行。本项目的最终目标是基于刺激相应型的纳米容器及其主客体化学的方法建立一个新颖的超分子绿色催化体系。

本项目"高效高选择性的动态超分子纳米容器绿色催化剂的开发"计划运用金属导向自组装方法来构筑系列配位超分子纳米容器体系，并基于主客体化学手段发展新型仿生催化剂。按照项目计划书，申请人在配位超分子纳米容器的设计组装、性能优化、刺激响应性调控、基于主客体识别基础之上的仿生催化等前沿领域开展了系统而深入的研究工作，并取得了重要进展。在过渡金属配位组装体系中拓展了逐级组装、诱导匹配自适应组装等方法，构筑了具有多重阴离子刺激响应、光致变色、氧化还原、及催化等功能的纳米管、动态大环、多面体型纳米容器；将稀土配位化学与超分子组装相结合，实现了多面体型稀土配位组装体系的可控合成，总结了手性稀土超分子体系的溶液配位组装规律，建立了稀土有机多面体发光调控策略，展示了配位超分子在高效的分子/离子识别传感方面的应用。近五年以通讯作者在Nature Commun., J. Am. Chem. Soc., Angew Chem.Int. Ed.等高水平期刊上发表论文15篇，培养博士研究生2名，硕士研究生3名。项目负责人多次受邀参加国内外学术会议，团队整体研究水平及影响力大幅提升。