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

Abstract

Active species regulation is a key scientific issue that essentially determines the selectivity and activity of a photocatalyst. Herein, Cu^I -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 %.