Stable Mn(II) metal–organic framework for efficient visible light initiated trifluoromethylation reaction

IF 6.5 1区化学 Q2 CHEMISTRY, PHYSICAL Journal of Catalysis Pub Date : 2024-06-03 DOI:10.1016/j.jcat.2024.115589

Xiong-Feng Ma , Bo Wen , Shaohui Zhang , Deshun Wang , Lele Wang , Huaxiang Lin , Zhaohui Li , Rusheng Yuan

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Abstract

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.

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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

合成了一种二维锰基 MOF（[Mn4(PDI)2(DMF)7(H2O)]n (MOF 1)）（H4PDI = 5,5′-(1,3,6,8-四氧代-1,3,6,8-四氢苯并[lmn][3,8]菲罗啉-2,7-二基)二间苯二甲酸）。可见光激发了 MOF 1 中的 Mn-PDI 单元，使 NaSO2CF3 氧化生成 CF3 自由基，从而使 MOF 1 在可见光下具有三氟甲基化（杂）烯烃的活性。MOF 1 在三氟甲基化反应中的异常稳定性可归因于其独特的结构，这种结构可防止其受到酸副产物的腐蚀。将 MOF 1 剥离成超薄纳米片或将 MOF 1 中的锰（II）部分氧化成锰（III），可得到 MOL 1 和 NB 1，它们在三氟甲基化反应中的活性显著提高，这表明催化剂的组成和形态对其性能具有重要作用。在这些锰基 MOF 上进行的光引发三氟甲基化反应被应用于多种基质。这项研究为三氟甲基化化合物的合成提供了一种有效的策略，并凸显了 MOFs 在光引发有机合成中的潜力。

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来源期刊

Journal of Catalysis 工程技术-工程：化工

CiteScore

12.30

自引率

5.50%

发文量

447

审稿时长

31 days

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.