ortho-Terphenylene Viologens with Through-Space Conjugation for Enhanced Photocatalytic Oxidative Coupling and Hydrogen Evolution

Ben He; Sikun Zhang; Yueyan Zhang; Guoping Li; Bingjie Zhang; Wenqiang Ma; Bin Rao; Ruitong Song; Lei Zhang; Yanfeng Zhang; Gang He

doi:10.1021/jacs.1c11577

ortho-Terphenylene Viologens with Through-Space Conjugation for Enhanced Photocatalytic Oxidative Coupling and Hydrogen Evolution

J Am Chem Soc. 2022 Mar 16;144(10):4422-4430. doi: 10.1021/jacs.1c11577. Epub 2022 Feb 10.

Authors

Ben He¹, Sikun Zhang², Yueyan Zhang², Guoping Li², Bingjie Zhang², Wenqiang Ma², Bin Rao¹, Ruitong Song², Lei Zhang³, Yanfeng Zhang¹, Gang He^{1

2}

Affiliations

¹ School of Chemistry, Xi'an Jiaotong University, Xi'an, Shaanxi Province 710049, People's Republic of China.
² Key Laboratory of Thermo-Fluid Science and Engineering of Ministry of Education, Frontier Institute of Science and Technology, State Key Laboratory for Strength and Vibration of Mechanical Structures, Xi'an Jiaotong University, Xi'an, Shaanxi Province 710054, People's Republic of China.
³ School of Optoelectronic Engineering, Xidian University, Xi'an, Shaanxi Province 710126, People's Republic of China.

PMID: 35143191
DOI: 10.1021/jacs.1c11577

Abstract

A series of novel ortho-terphenylene viologen derivatives (o-TPV²⁺) with through-space conjugation (TSC) via the combination of ortho-terphenylene skeletons with viologen structure is reported. Their optoelectronic properties can be adjusted by N-arylation or N-alkylation reactions. Compared with other viologen derivatives, o-TPV²⁺ not only exhibits strong photoluminescence but also retards the charge recombination process and stabilizes the diradical state without forming a quinoid structure due to the special TSC effect. Based on their special redox characteristics, o-TPV²⁺ was applied to the photocatalytic oxidative coupling of benzylamine with 96% yield. In addition, pTA-o-TPV²⁺ (tethered with p-toluic acid)-modified g-C₃N₄ was used for visible-light-driven hydrogen production for the first time, exceeding 15 times the rate over unmodified g-C₃N₄.