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Catalyst-free dynamic covalent Knoevenagel/amine condensation for the synthesis and optimization of Imine-linked covalent organic frameworks

delete2026-08-05
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PRE
AI
M
Mengying Lei
G
Ge Yan
D
Danlei Zhou
J
Jingwen Zhang
Y
Yao Lv
Z
Zhiqiang Wang
R
Ruirui Gu *
S
Sheng Dai *
H
He Tian
D
Da-Hui Qu *
DOI:10.1007/s11426-026-3426-0delete
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Abstract

Abstract

En 中文
With the rapid recent advances in constitutional dynamic chemistry (CDC), covalent organic frameworks (COFs), and dynamic polymers, the discovery and development of new dynamic covalent bonds have become a central priority, providing routes to novel architectures, controllable dynamic transformations, and emergent adaptive functions. Here, we report a facile, catalyst-free dynamic covalent condensation reaction between Knoevenagel derivatives (Kn) and amines that generate imines. Electron-withdrawing barbituric motifs intrinsically activate the carbon electrophile and lower the activation barrier relative to conventional aldehyde-amine condensations. The equilibrium constant (Keq) can be effectively tuned across three orders of magnitude by modulating the push-pull conjugation within the Kn reactants. We demonstrate that this reaction enables gram-scale COF synthesis under mild, catalyst-free, non-sealed conditions. Introducing electron-donating substituents on the Kn monomers effectively improves framework crystallinity and porosity. This Knoevenagel/amine condensation approach provides a clean, efficient, and tunable dynamic covalent platform for the development of COFs and constitutional dynamic libraries/materials.
Keywords:
dynamic covalent chemistry
polar olefin
Knoevenagel/amine condensation
covalent organic frameworks
dynamic covalent polymers

Journal

Science China-Chemistry cover
Science China-Chemistry
IF:
9.7
Papers:
5.4K
Citations:
1.5W

Organization

S
School of Chemistry and Molecular Engineering
Scholars:
184
Papers: 49
Citations: 0
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