1. Stable Mn(II) metal–organic framework for efficient visible light initiated trifluoromethylation reaction.
- Author
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Ma, Xiong-Feng, Wen, Bo, Zhang, Shaohui, Wang, Deshun, Wang, Lele, Lin, Huaxiang, Li, Zhaohui, and Yuan, Rusheng
- Subjects
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VISIBLE spectra , *METAL-organic frameworks , *PHOTOCATALYSTS , *RADICALS (Chemistry) , *PARTIAL oxidation , *ORGANIC synthesis - Abstract
[Display omitted] • A 2D Mn-based MOF (MOF 1) was synthesized and its structure was determined. • The visible light excited Mn-PDI unit in MOF 1 oxidizes NaSO 2 CF 3 to generate CF 3 radical for trifluoromethylation reactions. • The unusual stability of MOF 1 can be attributed to its unique structure to resist the corrosion by the acid byproduct. • 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 improved photocatalytic activity. A 2D Mn-based MOF ([Mn 4 (PDI) 2 (DMF) 7 (H 2 O)] n (MOF 1)) (H 4 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 MOF 1 oxidizes NaSO 2 CF 3 to generate CF 3 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. [ABSTRACT FROM AUTHOR]
- Published
- 2024
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