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

Active 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 (T4 EPE-Cu) with photo-regulated 1 O2 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 1 O2 via resonance energy transfer with Cu-alkynyl. For α-terpinene oxidation, the ratios of 1 O2 products to O2.- products can be controlled from 1.3 (380 nm) to 10.7 (600 nm). Furthermore, T4 EPE-Cu exhibited ultrahigh photocatalytic performance for Glaser coupling and benzylamine oxidation, with a conversion and selectivity of over 99 %.