Copper‐Bridged Tetrakis(4‐ethynylphenyl)ethene Aggregates with Photo‐Regulated 1O2 and O2.− Generation for Selective Photocatalytic Aerobic Oxidation

AbstractActive species regulation is a key scientific issue that essentially determines the selectivity and activity of a photocatalyst. Herein, CuI‐bridged tetrakis(4‐ethynylphenyl)ethene aggregates (T4EPE‐Cu) with photo‐regulated 1O2 and O2.− generation were demonstrated for selective photocatalytic aerobic oxidation. In this system, transient photovoltage combined with the density functional theory calculations confirmed that Cu‐alkynyl was the main oxygen activation site. The adsorbed O2 tends to produce O2.− because of the potential well effect of Cu‐alkynyl under high‐energy light excitation. But under low‐energy light, O2 tends to produce 1O2 via resonance energy transfer with Cu‐alkynyl. For α‐terpinene oxidation, the ratios of 1O2 products to O2.− products can be controlled from 1.3 (380 nm) to 10.7 (600 nm). Furthermore, T4EPE‐Cu exhibited ultrahigh photocatalytic performance for Glaser coupling and benzylamine oxidation, with a conversion and selectivity of over 99 %.