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论文类型：期刊论文

发表时间：2021-01-30

发表刊物：NATURE COMMUNICATIONS

卷号：9

期号：1

页面范围：4024

ISSN号：2041-1723

关键字：dye; polymer; thiophene; aromatic hydrocarbon; thiophene derivative, chemical reaction; drug; dye; electron; geometry; metabolism; oxidation; polymer; redox potential, Article; arylation; chemical interaction; chemical reaction; electron transport; geometry; methylation; molecular dynamics; oxidation reduction potential; photocatalysis; radical reaction; stereoselectivity; trifluoromethylation; chemistry; halogenation; methylation, Halogenation; Hydrocarbons, Aromatic; Methylation; Thiophenes

摘要：Direct trifluoromethylation of unactivated aromatic rings at metabolically susceptible positions is highly desirable in pharmaceutical applications. By incorporating thiophenes into the backbone of triphenylamine to enlarge its it-system, a new approach for constructing coordination polymers is reported for direct trifluoromethylation without prefunctionalization of the aryl precursors. The improved light-harvesting ability and well-modulated excited state redox potential of the designed polymers endow the generated CF3 radicals with suitable reactivity and enhance radical adduct oxidation in pores. The well-configurated interactions between the organic ligands distort the coordination geometry to create active interaction sites within the coordination polymer; thus, the substrates could be docked near the photoredox-active centres. The synergistic electronic and spatial effects in the confined pores balance the contradictory demands of electronic effects and reaction dynamics, achieving regio- and diastereoselective discrimination among reaction sites with unremarkable electronic/steric differences.