浙江大学黄宁研究组取得一项新突破。他们的研究开发出了三维共价有机框架高效光氧化还原催化原子转移自由基聚合的结构调控。该项研究成果发表在2025年2月10日出版的《德国应用化学》上。

在此，研究组设计并合成了一系列基于非那嗪的具有介质拓扑结构的功能三维COFs。通过取代基效应对COFs的渗透褶和能级进行结构调节。这些COFs可作为原子转移自由基聚合的有效光氧化还原催化剂。值得注意的是，具有三氟甲基取代基的COF比其他COFs具有更高的催化活性，可以有效合成分子量可控、分散性低、转化率高的聚合物。值得注意的是，它是所有无金属光催化剂中效率最高的一种。本研究不仅通过取代基效应实现了三维COFs的结构调控，而且在一系列具有挑战性的化学转化中，COFs作为高效催化剂具有良好的应用前景。

据介绍，共价有机骨架（COFs）在各种化学转化中已成为一类蓬勃发展的光催化剂。然而，利用COFs作为光氧化还原催化剂进行原子转移自由基聚合的研究却很少。

附：英文原文

Title: Structural Regulation of Three-Dimensional Covalent Organic Frameworks for Efficient Photoredox Catalysis toward Atom Transfer Radical Polymerization

Author: Sheng Niu, Zhenyang Hu, Xiaoyi Xu, Zuping Xiong, Hongzheng Chen, Alex K.-Y. Jen, Ning Huang

Issue&Volume: 2025-02-10

Abstract: Covalent organic frameworks (COFs) have emerged as a thriving class of photocatalysts in various chemical transformations. However, the utilization of COFs as photoredox catalysts for atom transfer radical polymerization is rarely known. Herein, we designed and synthesized a series of phenazine-based functional 3D COFs with the dia topology. Structural regulation over interpenetration folds and energy levels of COFs was implemented through the substituent effects. These COFs can work as effective photoredox catalysts toward atom transfer radical polymerization. Notably, the COF with trifluoromethyl substituent groups exhibits much higher catalytic activity than other COFs, allowing the efficient synthesis of polymers with controllable molecular weights, low dispersity, and high conversion. Notably, it constitutes the most efficient one among all the metal-free photocatalysts. This work not merely realizes the structural regulation of 3D COFs through substituent effects, but also exhibits brilliant prospects for the utilization of COFs as efficient catalysts in a bunch of challenging chemical transformations.

DOI: 10.1002/anie.202424860

Source: https://onlinelibrary.wiley.com/doi/10.1002/anie.202424860