Three-Dimensional Mesoporous Covalent Organic Framework for Photocatalytic Oxidative Dehydrogenation to Quinoline

Chou-Hung Hsueh; Chang He; Jiaqi Zhang; Xin Tan; Haojie Zhu; Weng-Chon Max Cheong; An-Zhen Li; Xin Chen; Haohong Duan; Yingbo Zhao; Chen Chen

doi:10.1021/jacs.4c12286

Three-Dimensional Mesoporous Covalent Organic Framework for Photocatalytic Oxidative Dehydrogenation to Quinoline

J Am Chem Soc. 2024 Dec 11;146(49):33857-33864. doi: 10.1021/jacs.4c12286. Epub 2024 Nov 28.

Authors

Chou-Hung Hsueh¹, Chang He^{1

2}, Jiaqi Zhang¹, Xin Tan¹, Haojie Zhu¹, Weng-Chon Max Cheong³, An-Zhen Li¹, Xin Chen⁴, Haohong Duan¹, Yingbo Zhao⁵, Chen Chen¹

Affiliations

¹ Engineering Research Center of Advanced Rare Earth Materials, Department of Chemistry, Tsinghua University, Beijing 100084, China.
² Institute of Molecular Engineering Plus, College of Chemistry, Fuzhou University, Fuzhou 350108, China.
³ Macao Institute of Materials Science and Engineering, Faculty of Innovation Engineering, Macau University of Science and Technology, Taipa, Macao SAR 999078, China.
⁴ Beijing Advanced Innovation Center for Materials Genome Engineering, Institute of Solid State Chemistry, University of Science and Technology Beijing, Beijing 100083, China.
⁵ School of Physical Science and Technology, Shanghai Key Laboratory of High-resolution Electron Microscopy, ShanghaiTech University, Shanghai 201210, China.

PMID: 39606862
DOI: 10.1021/jacs.4c12286

Abstract

Developing precious metal-free catalysts for organic reactions under mild conditions is urgent. Herein, we report a three-dimensional covalent organic framework (3D-COF) with high crystallinity and permanent pores, termed 3D-TABPA-COF, for the oxidation of tetrahydroquinoline to quinoline. The 3D-TABPA-COF assembled based on N₄,N₄-bis(4'-amino-[1,1'-biphenyl]-4-yl)-[1,1'-biphenyl]-4,4'-diamine (TABPA) is the catalytic active center for the conversion of tetrahydroquinoline. The triphenylamine in the structure is an effective photosensitizer, which not only enhances the light absorption capacity but also facilitates the rapid transfer of photogenerated electrons and ensures effective carrier separation. The obtained 3D-TABPA-COF has a high specific surface area (2745.06 m² g^-1) and mesopores of 3.57 nm. This is attributed to the fact that the bor topology is not easy to interpenetrate. It can oxidize tetrahydroquinoline to obtain quinoline efficiently under visible light irradiation. In addition, we also performed various photochemical characterizations combined with density functional theory calculations to elucidate the reaction mechanism from tetrahydroquinoline to quinoline. This work provides a feasible strategy for constructing 3D-COF to achieve efficient photocatalytic organic reactions.