Dye-incorporated coordination polymers for direct photocatalytic trifluoromethylation of aromatics at metabolically susceptible positions

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 π-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.

Synergistic photoredox and copper catalysis by diode-like coordination polymer with twisted and polar copper–dye conjugation

“…Noted that higher reorganisation energy was required for one-way electron transfer through the high-polar carboxylate–metal node in the most common carboxylate-based coordination polymers 16 . Moreover, as a versatile photosensitiser, triphenylamine ( TPA ) has been successfully modified into carboxylate-based coordination polymers to generate radicals by photoreduction 17 . Thus, the twisted conjugative connection of TPA -based ligand and polar carboxylate–copper node might realise the diode-like unidirectional electronic conductivity within coordination polymer for compromising photoredox and copper catalysis 18 .…”

Rational synthesis of interpenetrated 3D covalent organic frameworks for asymmetric photocatalysis

“…We selected triphenylamine as the functional molecule, since it represents a type of important hole-conducting molecule with unique photophysical and redox properties. 24 This led to the conclusion that the as-prepared 3D COFs can be used as photocatalysts for the cross-dehydrogenative coupling (CDC) reaction and the asymmetric α-alkylation of aldehydes integrated with a chiral imidazolidinone as the organocatalyst. 3 …”

Synthesis and Electronic Modulation of Nanostructured Layered Double Hydroxides for Efficient Electrochemical Oxygen Evolution

“…At present, the noble metals and noble metal‐based oxides are considered highly efficient OER electrocatalysts, but the scarcity and high cost have severely hindered their widespread commercial applications [14,16–18] . Besides noble metals‐based materials, it is also necessary to explore efficient, low‐cost, and stable non‐noble metal‐based OER electrocatalysts [19–23] .…”