Xiong-Feng Ma , Bo Wen , Shaohui Zhang , Deshun Wang , Lele Wang , Huaxiang Lin , Zhaohui Li , Rusheng Yuan
{"title":"用于可见光引发的高效三氟甲基化反应的稳定 Mn(II) 金属有机框架","authors":"Xiong-Feng Ma , Bo Wen , Shaohui Zhang , Deshun Wang , Lele Wang , Huaxiang Lin , Zhaohui Li , Rusheng Yuan","doi":"10.1016/j.jcat.2024.115589","DOIUrl":null,"url":null,"abstract":"<div><p>A 2D Mn-based MOF ([Mn<sub>4</sub>(PDI)<sub>2</sub>(DMF)<sub>7</sub>(H<sub>2</sub>O)]<sub>n</sub> (<strong>MOF 1</strong>)) (H<sub>4</sub>PDI = 5,5′-(1,3,6,8-tetraoxo-1,3,6,8-tetrahydrobenzo[lmn][3,8]phenanthroline-2,7-diyl)diisophthalic acid) was synthesized. Visible light excited Mn-PDI unit in <strong>MOF 1</strong> oxidizes NaSO<sub>2</sub>CF<sub>3</sub> to generate <sup><img></sup>CF<sub>3</sub> radical and enables <strong>MOF 1</strong> to exhibit activity for trifluoromethylation of (hetero)arenes under visible light. The unusual stability of <strong>MOF 1</strong> in the trifluoromethylation reactions can be attributed to its unique structure, which prevents it from corrosion by acid byproduct. The peeling of <strong>MOF 1</strong> to ultrathin nanosheets or partial oxidation of Mn(II) to Mn(III) in <strong>MOF 1</strong> led to <strong>MOL 1</strong> and <strong>NB 1</strong> with significant improved activity for trifluoromethylation reactions, demonstrating the important role of composition and morphology of a catalyst on its performance. The light initiated trifluoromethylation reactions over these Mn-based MOFs was applied to a variety of substrates. This study provides an efficient strategy for synthesis of trifluoromethylated compounds and highlights the potential of MOFs in light initiated organic syntheses.</p></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":null,"pages":null},"PeriodicalIF":6.5000,"publicationDate":"2024-06-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Stable Mn(II) metal–organic framework for efficient visible light initiated trifluoromethylation reaction\",\"authors\":\"Xiong-Feng Ma , Bo Wen , Shaohui Zhang , Deshun Wang , Lele Wang , Huaxiang Lin , Zhaohui Li , Rusheng Yuan\",\"doi\":\"10.1016/j.jcat.2024.115589\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><p>A 2D Mn-based MOF ([Mn<sub>4</sub>(PDI)<sub>2</sub>(DMF)<sub>7</sub>(H<sub>2</sub>O)]<sub>n</sub> (<strong>MOF 1</strong>)) (H<sub>4</sub>PDI = 5,5′-(1,3,6,8-tetraoxo-1,3,6,8-tetrahydrobenzo[lmn][3,8]phenanthroline-2,7-diyl)diisophthalic acid) was synthesized. Visible light excited Mn-PDI unit in <strong>MOF 1</strong> oxidizes NaSO<sub>2</sub>CF<sub>3</sub> to generate <sup><img></sup>CF<sub>3</sub> radical and enables <strong>MOF 1</strong> to exhibit activity for trifluoromethylation of (hetero)arenes under visible light. The unusual stability of <strong>MOF 1</strong> in the trifluoromethylation reactions can be attributed to its unique structure, which prevents it from corrosion by acid byproduct. The peeling of <strong>MOF 1</strong> to ultrathin nanosheets or partial oxidation of Mn(II) to Mn(III) in <strong>MOF 1</strong> led to <strong>MOL 1</strong> and <strong>NB 1</strong> with significant improved activity for trifluoromethylation reactions, demonstrating the important role of composition and morphology of a catalyst on its performance. The light initiated trifluoromethylation reactions over these Mn-based MOFs was applied to a variety of substrates. This study provides an efficient strategy for synthesis of trifluoromethylated compounds and highlights the potential of MOFs in light initiated organic syntheses.</p></div>\",\"PeriodicalId\":346,\"journal\":{\"name\":\"Journal of Catalysis\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":6.5000,\"publicationDate\":\"2024-06-03\",\"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/S0021951724003026\",\"RegionNum\":1,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"CHEMISTRY, PHYSICAL\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of Catalysis","FirstCategoryId":"92","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S0021951724003026","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
A 2D Mn-based MOF ([Mn4(PDI)2(DMF)7(H2O)]n (MOF 1)) (H4PDI = 5,5′-(1,3,6,8-tetraoxo-1,3,6,8-tetrahydrobenzo[lmn][3,8]phenanthroline-2,7-diyl)diisophthalic acid) was synthesized. Visible light excited Mn-PDI unit in MOF 1 oxidizes NaSO2CF3 to generate CF3 radical and enables MOF 1 to exhibit activity for trifluoromethylation of (hetero)arenes under visible light. The unusual stability of MOF 1 in the trifluoromethylation reactions can be attributed to its unique structure, which prevents it from corrosion by acid byproduct. The peeling of MOF 1 to ultrathin nanosheets or partial oxidation of Mn(II) to Mn(III) in MOF 1 led to MOL 1 and NB 1 with significant improved activity for trifluoromethylation reactions, demonstrating the important role of composition and morphology of a catalyst on its performance. The light initiated trifluoromethylation reactions over these Mn-based MOFs was applied to a variety of substrates. This study provides an efficient strategy for synthesis of trifluoromethylated compounds and highlights the potential of MOFs in light initiated organic syntheses.
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.