Building a Pyrazole–Benzothiadiazole–Pyrazole Photosensitizer into Metal–Organic Frameworks for Photocatalytic Aerobic Oxidation

作者：Ji‐Kang Jin, Kun Wu, Xin-Yi Liu, Guo‐Quan Huang, Yong‐Liang Huang, Dong Luo, Mo Xie, Yifang Zhao, Weigang Lu, Xiao‐Ping Zhou, Jian He, Dan Li · 发表于：Journal of the American Chemical Society · 年份：2021 · DOI：10.1021/jacs.1c10008 · 被引用次数：217 · 研究领域：Metal-Organic Frameworks: Synthesis and Applications、Advanced Photocatalysis Techniques、Covalent Organic Framework Applications

Charge separation plays a crucial role in regulating photochemical properties and therefore warrants consideration in designing photocatalysts. Metal–organic frameworks (MOFs) are emerging as promising candidates for heterogeneous photocatalysis due to their structural designability and tunability of photon absorption. Herein, we report the design of a pyrazole–benzothiadiazole–pyrazole organic molecule bearing a donor–acceptor–donor conjugated π-system for fast charge separation. Further attempts to integrate such a photosensitizer into MOFs afford a more effective heterogeneous photocatalyst (JNU-204). Under visible-light irradiation, three aerobic oxidation reactions involving different oxygenation pathways were achieved on JNU-204. Recycling experiments were conducted to demonstrate the stability and reusability of JNU-204 as a robust heterogeneous photocatalyst. Furthermore, we illustrate its applications in the facile synthesis of pyrrolo[2,1- a ]isoquinoline-containing heterocycles, core skeletons of a family of marine natural products. JNU-204 is an exemplary MOF platform with good photon absorption, suitable band gap, fast charge separation, and extraordinary chemical stability for proceeding with aerobic oxidation reactions under visible-light irradiation.