Release Time:2021-03-29  Hits:

Indexed by: Journal Article

Date of Publication: 2021-01-30

Journal: NATURE COMMUNICATIONS

Volume: 9

Issue: 1

Page Number: 4024

ISSN: 2041-1723

Key Words: 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

Abstract: 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.