Heteroatom‐Embedded Approach to Vinylene‐Linked Covalent Organic Frameworks with Isoelectronic Structures for Photoredox Catalysis

Embedding heteroatoms into the main backbones of polymeric materials has become an efficient tool for tailoring their structures and improving their properties. However, owing to comparatively harsh heteroatom‐doping conditions, this has rarely been explored in covalent organic frameworks (COFs). He...

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Published in:Angewandte Chemie International Edition 2022-02, Vol.61 (6), p.e202111627-n/a
Main Authors: Bi, Shuai, Zhang, Zixing, Meng, Fancheng, Wu, Dongqing, Chen, Jie‐Sheng, Zhang, Fan
Format: Article
Language:English
Subjects:
Aldehydes
Ammonia
Catalysis
covalent organic framework
Embedding
isoelectronic
Nitrogen atoms
Photoredox catalysis
Pyridines
pyrylium
Recyclability
Substitutes
vinylene linkage
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Summary:Embedding heteroatoms into the main backbones of polymeric materials has become an efficient tool for tailoring their structures and improving their properties. However, owing to comparatively harsh heteroatom‐doping conditions, this has rarely been explored in covalent organic frameworks (COFs). Herein, upon aldol condensation of a trimethyl‐substituted pyrylium salt with a tritopic aromatic aldehyde, a two‐dimensional oxonium‐embedded COF with vinylene linkages was achieved, which was further converted to a neutral pyridine‐cored COF by in situ replacement of oxonium ions with nitrogen atoms under ammonia treatment. The two heteroatom‐embedded COFs are conceptually isoelectronic with each other, featuring similar geometric structures but different electronic structures, rendering them capable of catalyzing the visible‐light‐promoted multi‐component synthesis of tri‐substituted pyridine derivatives with good recyclability. A two‐dimensional oxonium‐embedded COF with vinylene linkages was synthesized by condensation of a trimethyl‐substituted pyrylium with a tritopic aromatic aldehyde derivative, which was readily converted to a neutral pyridine‐cored COF by in situ replacing oxonium with nitrogen atoms under the treatment of ammonia.
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.202111627