{"title":"Stable bio-inspired Mn4O4 cubic molecular photo catalyst for effective visible light-driven C–H direct trifluoromethylation","authors":"Shujing Li, Ke Li, Wenjie Shi, Keren He, Han Xie","doi":"10.1016/j.jcat.2025.116106","DOIUrl":null,"url":null,"abstract":"<div><div>Inspired by the natural oxygen-evolving complex of photosystem II with a cubic Mn<sub>4</sub>CaO<sub>5</sub> cluster, there is relatively little research on photo catalysts that closely resemble the cubic Mn<sub>4</sub>CaO<sub>5</sub> cluster. Therefore, the development of mixed-valence Mn<sub>4</sub>CaO<sub>5</sub> simulacrums has sparked great interest. Herein, we successfully obtained a Mn<sub>4</sub>O<sub>4</sub> cubic cluster with [Mn<sub>4</sub>(<em>mbm</em>)<sub>4</sub>(CH<sub>3</sub>CH<sub>2</sub>OH)<sub>4</sub>Br<sub>4</sub>]·[Mn<sub>4</sub>(<em>mbm</em>)<sub>4</sub>(CH<sub>3</sub>CH<sub>2</sub>OH)<sub>3</sub>(H<sub>2</sub>O)Br<sub>4</sub>] (<strong>Mn<sub>4</sub>Br</strong>) by using MnBr<sub>2</sub> and 1-Me-benzo[d]imidazol-2-yl)methanolate (H<em>mbm</em>) with its structure determined by single crystal crystallography. The Mn<sub>4</sub>O<sub>4</sub> cubic cores consists of an octahedral Mn(II) center chelated by the alkoxide oxygen and imidazole nitrogen atoms from monoanionic <em>mbm</em><sup>−</sup> and coordinated by alcohol/H<sub>2</sub>O and bromide ion. <strong>Mn<sub>4</sub>Br</strong> was found to exhibit activity for trifluoromethylation reaction under visible light. The oxidization of <strong>Mn<sub>4</sub>Br</strong> under I<sub>2</sub> solution led to the formation of mix-valent <strong>Mn<sub>4</sub>Br-I<sub>2</sub></strong> with smallest sizes, which exhibited improved much higher activity for the C–H activated trifluoromethylation reaction due to the much higher redox performance as well as a lower charge-transfer resistance. This study provides a new and efficient strategy for the synthesis of Mn<sub>4</sub>CaO<sub>4</sub> simulacrum structures with mixed valent states and develops its application in photocatalytic organic synthesis.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"447 ","pages":"Article 116106"},"PeriodicalIF":6.5000,"publicationDate":"2025-03-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of Catalysis","FirstCategoryId":"92","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S002195172500171X","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
引用次数: 0
Abstract
Inspired by the natural oxygen-evolving complex of photosystem II with a cubic Mn4CaO5 cluster, there is relatively little research on photo catalysts that closely resemble the cubic Mn4CaO5 cluster. Therefore, the development of mixed-valence Mn4CaO5 simulacrums has sparked great interest. Herein, we successfully obtained a Mn4O4 cubic cluster with [Mn4(mbm)4(CH3CH2OH)4Br4]·[Mn4(mbm)4(CH3CH2OH)3(H2O)Br4] (Mn4Br) by using MnBr2 and 1-Me-benzo[d]imidazol-2-yl)methanolate (Hmbm) with its structure determined by single crystal crystallography. The Mn4O4 cubic cores consists of an octahedral Mn(II) center chelated by the alkoxide oxygen and imidazole nitrogen atoms from monoanionic mbm− and coordinated by alcohol/H2O and bromide ion. Mn4Br was found to exhibit activity for trifluoromethylation reaction under visible light. The oxidization of Mn4Br under I2 solution led to the formation of mix-valent Mn4Br-I2 with smallest sizes, which exhibited improved much higher activity for the C–H activated trifluoromethylation reaction due to the much higher redox performance as well as a lower charge-transfer resistance. This study provides a new and efficient strategy for the synthesis of Mn4CaO4 simulacrum structures with mixed valent states and develops its application in photocatalytic organic synthesis.
期刊介绍:
The Journal of Catalysis publishes scholarly articles on both heterogeneous and homogeneous catalysis, covering a wide range of chemical transformations. These include various types of catalysis, such as those mediated by photons, plasmons, and electrons. The focus of the studies is to understand the relationship between catalytic function and the underlying chemical properties of surfaces and metal complexes.
The articles in the journal offer innovative concepts and explore the synthesis and kinetics of inorganic solids and homogeneous complexes. Furthermore, they discuss spectroscopic techniques for characterizing catalysts, investigate the interaction of probes and reacting species with catalysts, and employ theoretical methods.
The research presented in the journal should have direct relevance to the field of catalytic processes, addressing either fundamental aspects or applications of catalysis.