Zhao Zhenghua, Liu Mingjie, Zhou Kai, Guo Lidong, Shen Yajing, Lu Dan, Hong Xin, Bao Zongbi, Yang Qiwei, Ren Qilong, Schreiner Peter R, Zhang Zhiguo
Key Laboratory of Biomass Chemical Engineering of Ministry of Education, College of Chemical and Biological Engineering, Zhejiang University, Hangzhou 310058, P. R. China.
Institute of Zhejiang University-Quzhou, Quzhou 324000, P. R. China.
ACS Appl Mater Interfaces. 2023 Feb 8;15(5):6982-6989. doi: 10.1021/acsami.2c21304. Epub 2023 Jan 30.
Phenoxyl radicals originating from phenols through oxidation or photoinduction are relatively stable and exhibit mild oxidative activity, which endows them with the potential for photocatalysis. Herein, a stable and recyclable metal-organic framework constructed of a binaphthol derivative ligand has been synthesized and functions as an efficient heterogeneous photocatalyst. shows fairly good catalytic activity and substrate compatibility toward the selective oxidation of sulfides to sulfoxides under visible light irradiation. Such irradiation of converts the phenolic hydroxyl groups of the binaphthol derivative ligand to phenoxyl radicals through excited state intramolecular proton transfer, and the excited state photocatalyst triggers the single-electron oxidation of the sulfide. No reactive oxygen species are produced in the photocatalytic process, and triplet O directly participates in the reaction, endowing with wide substrate compatibility and high selectivity, which also proposes a promising pathway for the direct activation of substrates via phenoxyl radicals.
通过氧化或光诱导从酚类产生的苯氧基自由基相对稳定，并表现出温和的氧化活性，这赋予它们光催化的潜力。在此，由联萘酚衍生物配体构建的一种稳定且可回收的金属有机框架已被合成，并作为一种高效的多相光催化剂发挥作用。在可见光照射下，该催化剂对硫化物选择性氧化为亚砜表现出相当好的催化活性和底物兼容性。这种照射通过激发态分子内质子转移将联萘酚衍生物配体的酚羟基转化为苯氧基自由基，并且激发态光催化剂引发硫化物的单电子氧化。在光催化过程中不产生活性氧物种，三线态氧直接参与反应，赋予该催化剂广泛的底物兼容性和高选择性，这也为通过苯氧基自由基直接活化底物提出了一条有前景的途径。
