Wang Qian-You, Liu Jing, Cao Man, Hu Jia-Hua, Pang Rui, Wang Shan, Asad Muhammad, Wei Yong-Li, Zang Shuang-Quan
Henan Key Laboratory of Crystalline Molecular Functional Materials, Green Catalysis Center, and College of Chemistry, Zhengzhou University, Zhengzhou, 450001, China.
International Laboratory for Quantum Functional Materials of Henan, School of Physics and Microelectronics, Zhengzhou University, Zhengzhou, 450001, China.
Angew Chem Int Ed Engl. 2022 Aug 8;61(32):e202207130. doi: 10.1002/anie.202207130. Epub 2022 Jun 28.
Covalent organic frameworks (COFs) are appealing photocatalysts for toxic chemical degradation. Great efforts have been devoted to regulate the photocatalytic performance of COFs by tuning their organic building blocks, but the relationship between COF linkage and photochemical properties has rarely been explored. Herein, we report the synthesis and characterisation of a novel aminal-linked porphyrinic COF, namely Por-Aminal-COF. Por-Aminal-COF (0.25 mol %) showed excellent photocatalytic activity toward the detoxification of the sulfur mustard simulant with a half-life (t ) of 5 min, which is far lower than that of traditional imine-linked Por-COF (t =16 min). Transient absorption spectroscopy indicated that the aminal linkages of Por-Aminal-COF facilitated the intersystem crossing process. Thus, Por-Aminal-COF showed higher triplet-state generation efficiency compared with Por-COF, consequently promoting the activation of oxygen molecular to singlet oxygen.
共价有机框架（COFs）是用于有毒化学物质降解的有吸引力的光催化剂。人们已经付出了巨大努力通过调整其有机结构单元来调节COFs的光催化性能，但COF连接与光化学性质之间的关系很少被探索。在此，我们报道了一种新型氨基连接的卟啉COF，即Por-Aminal-COF的合成与表征。Por-Aminal-COF（0.25 mol %）对硫芥模拟物的解毒表现出优异的光催化活性，半衰期（t ）为5分钟，远低于传统亚胺连接的Por-COF（t =16分钟）。瞬态吸收光谱表明Por-Aminal-COF的氨基连接促进了系间窜越过程。因此，与Por-COF相比，Por-Aminal-COF表现出更高的三重态产生效率，从而促进了氧分子向单线态氧的活化。
