Chromophore‐Inspired Design of Pyridinium‐Based Metal–Organic Polymers for Dual Photoredox Catalysis

Abstract

Abstract2,4,6‐Triphenylpyrylium (TPT+) functions as a classic organic photocatalyst and exhibits a noteworthy absorption in the visible range, strongly oxidizing excited states, and a somewhat unstable structure. Inspired by the nuclear chromophore and dual catalysis strategy, herein, we report a universal photoredox platform constructed by TPT+‐mimic bridging ligands and reductive metal ions on the basis of metal–organic supramolecular systems for various organic couplings and molecular oxygen activation under visible‐light irradiation. Significant photoinduced electron transfer and ligand‐to‐metal charge‐transfer events are both integrated and regulated by the spatial and kinetic confinement effects of the structurally confined microenvironments, effectively improving the efficiency of electron transfer and radical–radical coupling processes in photocatalysis. This package deal provides a promising way for the design of novel photocatalysts and the development of versatile and sustainable synthetic chemistry.