Wang Yuancheng, Hao Wenbo, Liu Hui, Chen Renzeng, Pan Qingyan, Li Zhibo, Zhao Yingjie
College of Polymer Science and Engineering, Qingdao University of Science and Technology, Qingdao, 266042, China.
Nat Commun. 2022 Jan 10;13(1):100. doi: 10.1038/s41467-021-27573-1.
Developing a facile strategy for the construction of vinylene-linked fully π-conjugated covalent organic frameworks (COFs) remains a huge challenge. Here, a versatile condition of Knoevenagel polycondensation for constructing vinylene-linked 2D COFs was explored. Three new examples of vinylene-linked 2D COFs (BTH-1, 2, 3) containing benzobisthiazoles units as functional groups were successfully prepared under this versatile and mild condition. The electron-deficient benzobisthiazole units and cyano-vinylene linkages were both integrated into the π conjugated COFs skeleton and acted as acceptor moieties. Interestingly, we found the construction of a highly ordered and conjugated D-A system is favorable for photocatalytic activity. BTH-3 with benzotrithiophene as the donor with a strong D-A effect exhibited an attractive photocatalytic HER of 15.1 mmol hg under visible light irradiation.
开发一种简便的策略来构建亚乙烯基连接的全π共轭共价有机框架（COF）仍然是一个巨大的挑战。在此，探索了用于构建亚乙烯基连接的二维COF的Knoevenagel缩聚的通用条件。在这种通用且温和的条件下，成功制备了三个以苯并双噻唑单元为官能团的亚乙烯基连接的二维COF（BTH-1、2、3）的新实例。缺电子的苯并双噻唑单元和氰基亚乙烯基连接均整合到π共轭COF骨架中，并充当受体部分。有趣的是，我们发现构建高度有序的共轭给体-受体（D-A）体系有利于光催化活性。以苯并三噻吩为给体且具有强D-A效应的BTH-3在可见光照射下表现出15.1 mmol hg的诱人光催化析氢反应活性。
