文献类型：期刊文献

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

作者：Lei, Mengying[1,2];Yan, Ge[1,2];Zhou, Danlei[1,2];Zhang, Jingwen[1,2];Lv, Yao[1,2];Wang, Zhiqiang[3];Gu, Ruirui[1,2];Dai, Sheng[1,2];Tian, He[1,2];Qu, Da-Hui[1,2]

机构：[1]East China Univ Sci & Technol, Feringa Nobel Prize Scientist Joint Res Ctr, Frontiers Sci Ctr Materiobiol & Dynam Chem, Key Lab Adv Mat,Sch Chem & Mol Engn,Inst Fine Chem, Shanghai 200237, Peoples R China;[2]East China Univ Sci & Technol, Joint Int Res Lab Precis Chem & Mol Engn, Frontiers Sci Ctr Materiobiol & Dynam Chem,Inst Fi, Feringa Nobel Prize Scientist Joint Res Ctr,Sch Ch, Shanghai 200237, Peoples R China;[3]East China Univ Sci & Technol, Sch Chem & Mol Engn, State Key Lab Green Chem Engn & Ind Catalysis, Shanghai 200237, Peoples R China

年份：2026

外文期刊名：SCIENCE CHINA-CHEMISTRY

收录：;EI(收录号：20263221270492);Scopus(收录号：2-s2.0-105046774955);WOS:【SCI-EXPANDED(收录号:WOS:001841869600001)】；

基金：This work was supported by the National Natural Science Foundation of China (22588101, 22571084, 22220102004), the Fundamental and Interdisciplinary Disciplines Breakthrough Plan of the Ministry of Education of China (JYB2025XDXM404), the Science and Technology Commission of Shanghai Municipality (24DX1400200), the Innovation Program of Shanghai Municipal Education Commission (2023ZKZD40), the Program of Introducing Talents of Discipline to Universities (B16017), the Shanghai Natural Science Foundation Project (23JC1401700), the Fundamental Research Funds for the Central Universities, the Guangxi Science and Technology Innovation Platform Program (Leitai Action Plan-Guangxi Laboratory Capacity Building) (LT2504240013) and the China National Petroleum Corporation (CNPC) Innovation Fund (2024DQ02-0410).

语种：英文

外文关键词：dynamic covalent chemistry; polar olefin; Knoevenagel/amine condensation; covalent organic frameworks; dynamic covalent polymers

摘要：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 (K eq) 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.