Lu Zhen, Zhao Rui, Yang Hongjie, Fu Xiaoling, Zhao Yulai, Xiao Longqiang, Hou Linxi
Qingyuan Innovation Laboratory, Quanzhou, 362801, P. R. China.
College of Chemistry, Fuzhou University, No. 2 Xueyuan Road, Fuzhou, 350116, P. R. China.
Angew Chem Int Ed Engl. 2022 Oct 24;61(43):e202208898. doi: 10.1002/anie.202208898. Epub 2022 Aug 30.
Two imine-based covalent organic framework photocatalysts with different building units, TPB-DMTA-COF and TAT-DMTA-COF, for photo-induced energy transfer reversible complexation-mediated radical polymerization (PET-RCMP) were developed and investigated, producing ideal polymers with accurate molecular weight and moderate dispersity under visible light irradiation. The chain extension and spatiotemporal control experiments revealed the high chain-end fidelity of polymers and the compatibility of RCMP processes in both bulk and aqueous system. Moreover, density functional theory (DFT) calculations verified that heteroatom-doped TAT-DMTA-COF exhibits higher activities for weakening C-I bond energy barrier, which promotes PET-RCMP polymerization performance. This work demonstrates that rational adjustment of building block for constructing COF heterogeneous photocatalyst can enhance the catalytic performance of PET-RCMP, providing a design methodology for the development of polymeric organic photoelectric semiconductor catalysts to mediate RCMP.
开发并研究了两种具有不同结构单元的基于亚胺的共价有机框架光催化剂TPB-DMTA-COF和TAT-DMTA-COF，用于光诱导能量转移可逆络合介导的自由基聚合（PET-RCMP），在可见光照射下可制备出具有精确分子量和适度分散性的理想聚合物。扩链和时空控制实验揭示了聚合物的高链端保真度以及RCMP过程在本体和水体系中的兼容性。此外，密度泛函理论（DFT）计算证实，杂原子掺杂的TAT-DMTA-COF在削弱C-I键能垒方面表现出更高的活性，这促进了PET-RCMP聚合性能。这项工作表明，合理调整构建COF非均相光催化剂的结构单元可以提高PET-RCMP的催化性能，为开发用于介导RCMP的聚合物有机光电半导体催化剂提供了一种设计方法。
