基于均苯三甲酰胺骨架的超分子催化剂的构筑及其催化性能研究

Supramolecular catalyss, which has benefited from the development of both homogeneous catalysis and supramolecular chemistry, has become an important frontier of research in recent years. In this project, we will focus on the design, preparation and application of a new kind of supramolecular catalysts based on the well-studied benzene-1,3,5-tricarboxamide (BTA) motif. Unlike the preparation of traditional homogeneous catalysts and immobilized catalysts, these supramolecular catalysts will be fabricated through rational design of the functionalized BTA molecules and precisely controlling the arrangement of the catalytically active units by a self-assembly process. Such new kind of catalysts are thus expected to exhibit better catalytic performance as compared with the traditional homogeneous catalytic systems, due to the unique "microenvironment effects" (such as cooperation effect, isolation effect, and chiral amplification effect). In addition, the relationship between the catalytic property and the tunable microenvironment created by the supramolecular catalysts will be systematically investigated. This research will further open up a new avenue for the fabrication of new supramolecular catalysts and promote the development of supramolecular catalysis.

利用超分子识别与组装的基本原理，发展新型超分子催化剂及实现催化反应的超分子选择性调控是催化领域新的研究热点和前沿。本项目将突破传统均相催化剂和负载催化剂的设计思路，运用超分子化学中分子识别与自组装以及模拟酶催化的原理，选择组装性能优异和功能化修饰方便的均苯三甲酰胺衍生物为组装基元，通过精确的分子设计和组装模式控制，构筑出一类具有独特微环境效应（协同效应、孤立效应以及手性诱导与放大效应等）的多功能超分子催化体系，以克服传统均相催化剂和负载催化剂效率低和选择性差的缺点（如均相催化体系中的二聚失活、配位饱和以及缺少协同作用等），为新型（手性）超分子催化剂的构筑提供新途径，促进超分子催化研究的发展。

本项目以功能导向的多层次有序超分子体系的构筑及其应用为指导目标，发展了一些催化功能导向的多层次有序超分子体系的高效构筑方法，建立了两类可控自组装协同催化的超分子催化新体系，并成功的应用于不对称Henry反应和烯烃环氧化反应中，取得了不错的催化效果，同时阐释有序超分子体系结构-催化性能的构效关系，为新型（手性）超分子催化剂的构筑提供新途径，促进超分子催化研究的发展。在此基础上，进一步利用C3v这一独特分子结构的协同放大效应实现弱C-H/pai弱相互作用力作为主要驱动力构筑了稳定的凝胶体系，同时研究了基于手性树状分子螺旋自组装，成功制备了螺旋结构可控的手性树状分子凝胶材料，实现了多层系自组装结构中超分子手性的产生、传递和放大，并利用“将军与士兵”原则和“大多数”原则成功诱导和控制了螺旋组装体的手性构型。