Ternary supramolecular system for photocatalytic oxidation with air by consecutive photo-induced electron transfer processes

Developing new photocatalysts for settling the tightest bottlenecks that lower efficiency, inferior selectivity and harsh conditions in organic oxidation reactions with air is very significant. Herein, ZnW–DPNDI–PYI was achieved by assembling a functional photosensitizer, an oxidation catalyst [BW12O40]5−, and an organocatalyst into one single framework. The anion⋯π and NH⋯O hydrogen bonds interactions facilitate the consecutive photo-induced electron transfer (conPET) process for the photocatalytic oxidation by stabilizing the radical-anion intermediate and catalyst-substrate interacted moiety. Besides, N,N′-bis(4-pyridylmethyl)naphthalene diimide (DPNDI) can be excited by visible light, the photogenerated electron and hole would further activate oxygen and substrates, respectively, to give the corresponding redox products. High conversion and selectivity of ZnW–DPNDI–PYI in photocatalytic coupling of primary amines and olefins epoxidation with air under visible-light have been demonstrated.