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Three‐Dimensional Radical Covalent Organic Frameworks as Highly Efficient and Stable Catalysts for Selective Oxidation of Alcohols
Author(s) -
Chen Fengqian,
Guan Xinyu,
Li Hui,
Ding Jiehua,
Zhu Liangkui,
Tang Bin,
Valtchev Valentin,
Yan Yushan,
Qiu Shilun,
Fang Qianrong
Publication year - 2021
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.202108357
Subject(s) - catalysis , radical , covalent bond , chemistry , alcohol oxidation , redox , covalent organic framework , surface modification , combinatorial chemistry , functional group , chemical engineering , nanotechnology , materials science , organic chemistry , polymer , engineering
With excellent designability, large accessible inner surface, and high chemical stability, covalent organic frameworks (COFs) are promising candidates as metal‐free heterogeneous catalysts. Here, we report two 3D radical‐based COFs (JUC‐565 and JUC‐566) in which radical moieties (TEMPO) are uniformly decorated on the channel walls via a bottom‐up approach. Based on grafted functional groups and suitable regular channels, these materials open up the application of COFs as highly efficient and selective metal‐free redox catalysts in aerobic oxidation of alcohols to relevant aldehydes or ketones with outstanding turn over frequency (TOF) up to 132 h −1 , which has exceeded other TEMPO‐modified catalytic materials tested under similar conditions. These stable COF‐based catalysts could be easily recovered and reused for multiple runs. This study promotes potential applications of 3D functional COFs anchored with stable radicals in organic synthesis and material science.