Copper‐Bridged Tetrakis(4‐ethynylphenyl)ethene Aggregates with Photo‐Regulated <sup>1</sup>O<sub>2</sub> and O<sub>2</sub><sup>.−</sup> Generation for Selective Photocatalytic Aerobic Oxidation
Huiying Sun, Zhongling Lang, Yingnan Zhao, Xinyu Zhao, Tianyu Qiu, Hong Qiang, Kaiqiang Wei, Huaqiao Tan, Zhenhui Kang, Yangguang Li
Abstract
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 (T 4 EPE‐Cu) with photo‐regulated 1 O 2 and O 2 .− 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 O 2 tends to produce O 2 .− because of the potential well effect of Cu‐alkynyl under high‐energy light excitation. But under low‐energy light, O 2 tends to produce 1 O 2 via resonance energy transfer with Cu‐alkynyl. For α‐terpinene oxidation, the ratios of 1 O 2 products to O 2 .− products can be controlled from 1.3 (380 nm) to 10.7 (600 nm). Furthermore, T 4 EPE‐Cu exhibited ultrahigh photocatalytic performance for Glaser coupling and benzylamine oxidation, with a conversion and selectivity of over 99 %.