功能多孔有机聚合物的设计合成及其不对称可见光光氧化还原催化性能研究

Visible-light photoredox catalysis has been an effective way to drive chemical transformations, it plays an important role in the development of the organic synthesis. However, the control of enantioselectivity in this type of reactions remains especially a challenge. Dual-catalyst approach is usually employed to achieve the enantioselectivity in the visible-light photoredox catalytic reactions. But, the transition metal-based photocatalysts are potentially toxic to contaminate the products and overall unsustainable, and the relatively high loading of chiral reagents is also a waste of resources. Moreover, it is difficult to separate the products from the homogeneous systems. The major objective of this project is to develop solid state photocatalyst systems for enantioselective visible-light photoredox catalysis. Combining the advantages of high stability, substantial porosity and large surface areas of the porous organic polymers with the metal-free synthetic methods, we plan to design and synthesize a class of all-organic solid state porous polymers which endowed both chiral functions and photosensitive groups. To investigate and control the microstructures of the porous organic frameworks, we will systematically modify the monomers, the chemical functions and the reaction conditions. Different types of photoredox catalytic reactions will be selected here to evaluate the enantioselectivity and the catalytic efficiency of the target porous polymer catalysts. Furthermore, the relationship between the structures of polymer catalysts and their catalytic properties will be revealed. The proposed study will provide new strategies for the development of heterogeneous enantioselective visible-light photoredox catalysts. It is also of great importance to broaden the applications of porous organic polymers.

可见光光氧化还原催化作为一种高效绿色的催化方式对有机合成的发展意义重大。然而在此类催化反应中控制反应产物的对映选择性仍十分困难。目前，常用的双催化剂体系存在金属污染，手性辅助试剂过量使用及均相体系难分离等缺点。本项目旨在开发能有效应用于对映选择性可见光光氧化还原反应的单一异相催化剂体系。课题将结合多孔有机聚合物稳定性高、孔洞丰富、比表面积大等特点，运用无金属参与的合成方法制备一系列兼具手性及光敏特性的多孔有机聚合物。通过系统地改变单体种类、功能基团引入量和反应条件等来调控聚合物微观结构；利用不同探针催化反应，考察可见光照射下，目标多孔有机聚合物在分子对映选择性合成中的催化能力；研究并构建材料结构与催化性能间的关系。本项目的实施将为开发新型的异相对映选择性光氧化还原催化体系提供新的研究思路，同时对拓宽多孔有机聚合物的应用范围具有重要意义。

多孔有机聚合物的固相本性、高稳定性、丰富的孔功能及大比表面积对拓展新型多孔材料的应用有着重要意义。本项目围绕多孔聚合物材料，综合利用有机合成化学、固体化学及晶体学等多个领域的研究方法，通过改变功能有机单体分子的大小、官能团种类、反应条件等，实现了具有不同孔径、不同比表面积、不同形貌的多孔聚合物材料的功能化靶向设计合成。项目系统地研究了多孔聚合物材料的合成策略，开发了无金属催化、纯水相合成及室温合成等多种简易制备方法；同时，结合材料结构与性能的关系，通过探针催化反应系统地探究了多孔有机聚合物的异相催化能力。此外，基于所合成的功能化单体分子，拓展制备了多个多孔配位聚合物材料，并系统地研究了其在小分子吸附、催化、荧光检测及电化学等方面的应用。本研究为开发特定功能的新型固相多孔聚合物材料提供了参考思路，对固体化学及材料科学的发展也有着重要意义。