Multi-Electron Visible Light Photoaccumulation on a Dipyridylamine Copper(II)–Polyoxometalate Conjugate Applied to Photocatalytic Generation of CF₃ Radicals

Abstract

This article describes the synthesis and characterization of an organic–inorganic hybrid polyoxometalate functionalized by a short link with a tripodal N-based ligand and its copper complex. Upon visible light irradiation, the latter is able to store up to three reducing equivalents. The locus of the reduction is discussed based on physicochemical measurements and DFT calculations. In the presence of Togni’s reagent, this complex allows for the photocatalytic generation of CF3 radicals, opening the road to valuable synthetic applications.

Efficient Trifluoromethylation of Halogenated Hydrocarbons Using Novel [(bpy)Cu(O2CCF2SO2F)2] Reagent

“…Consequently, the development of efficient and selective trifluoromethylating agents has been a focal point of research, aiming to achieve precise control over the incorporation of this moiety into target molecules. Recent advancements have seen the emergence of novel reagents and methodologies that facilitate the trifluoromethylation of a wide range of substrates under milder and more environmentally sustainable conditions [ 12 , 13 , 14 , 15 , 16 , 17 , 18 , 19 , 20 , 21 , 22 , 23 , 24 , 25 , 26 , 27 , 28 , 29 ]. For instance, the development of photoredox catalysis [ 12 , 13 , 14 , 15 ] and the use of less toxic and more readily available sources of the trifluoromethyl group [ 17 , 24 ] have marked significant milestones in this arena.…”

“…Recent advancements have seen the emergence of novel reagents and methodologies that facilitate the trifluoromethylation of a wide range of substrates under milder and more environmentally sustainable conditions [ 12 , 13 , 14 , 15 , 16 , 17 , 18 , 19 , 20 , 21 , 22 , 23 , 24 , 25 , 26 , 27 , 28 , 29 ]. For instance, the development of photoredox catalysis [ 12 , 13 , 14 , 15 ] and the use of less toxic and more readily available sources of the trifluoromethyl group [ 17 , 24 ] have marked significant milestones in this arena. As such, the ongoing research and development in this field continue to expand the toolkit of synthetic chemists, enabling the more widespread application of the trifluoromethyl group in organic synthesis.…”

A series of isopolymolybdate–viologen hybrids with photo-, thermo- and electro-chromic properties

“…Polyoxometalates (POMs), as a large class of anionic clusters with diverse structures, are polynuclear complexes composed of {MO x } polyhedra with classical V V , Nb V , Ta V , Mo VI or W VI atoms sharing edges and angles. 1–3 The size, shape and configuration of POMs are controllable, and they have a precise chemical composition and topological structure. 4–6 In the past few decades, many POMs with a novel structure and attractive performance have been developed and studied in many application fields.…”