Stepwise Conjugation Extension of Covalent Organic Frameworks via Multicomponent Linkage Conversion for Optimized Photocatalytic Molecular Oxygen Activation
Abstract
ABSTRACT Conjugated covalent organic frameworks (COFs) have emerged as a promising class of semiconducting heterogeneous photocatalysts. Precise control of the conjugation within their framework is pivotal for tuning electronic structures and optimizing catalytic performance, yet conventional approaches for linker extension face significant synthetic limitations. We report in this work a multicomponent reaction strategy that enables stepwise tuning of the conjugation of COFs through linkage conversion, where imine linkages are sequentially transformed into tetrahydrophenanthridine and further into phenanthridine units. The progressively extended conjugation results in a lower bandgap and reduced exciton binding energy, thereby promoting light harvesting and subsequent free charge carrier generation and utilization. Among the COFs bearing different linkages, the phenanthridine‐linked COF exhibits superior efficiency in photocatalytic activation of molecular oxygen for a variety of chemical transformations, including hydrogen peroxide generation, thioether oxidation, and benzimidazole synthesis under mild conditions.
Article Details
Authors (10)
Shu‐Xin Chen
Spin‐X Institute School of Chemistry and Chemical Engineering School of Biomedical Sciences and Engineering Guangdong‐Hong Kong‐Macao Joint Laboratory of Optoelectronic and Magnetic Functional Materials State Key Laboratory of Luminescent Materials and Devices South China University of Technology Guangzhou China
Xinglin Cao
Dongguan Key Laboratory of Interdisciplinary Science For Advanced Materials and Large‐Scale Scientific Facilities School of Physical Sciences Great Bay University Dongguan China
Mingcong Wang
Dongguan Key Laboratory of Interdisciplinary Science For Advanced Materials and Large‐Scale Scientific Facilities School of Physical Sciences Great Bay University Dongguan China
Sizhuo Yang
Zhiyuan Huang
The Molecular Foundry
Cameron Wilson
Peyman Z. Moghadam
Department of Chemical Engineering University College London London UK
Yingying Ning
Spin-X Institute, School of Chemistry and Chemical Engineering, School of Biomedical Sciences and Engineering, Guangdong-Hong Kong-Macao Joint Laboratory of Optoelectronic and Magnetic Functional Materials, State Key Laboratory of Luminescent Materials and Devices
Yi Liu
Jiyun Hu
Dongguan Key Laboratory of Interdisciplinary Science for Advanced Materials and Large-Scale Scientific Facilities, School of Physical Science