biostudies-literatureZhang WEngineering and Physical Sciences Research Council72-79https://www.ebi.ac.uk/biostudies/studies/S-EPMC8986529biostudies-literatureUnknown604(7904)Covalent organic frameworks (COFs) are distinguished from other organic polymers by their crystallinity^1-3, but it remains challenging to obtain robust, highly crystalline COFs because the framework-forming reactions are poorly reversible^4,5. More reversible chemistry can improve crystallinity^6-9, but this typically yields COFs with poor physicochemical stability and limited application scope⁵. Here we report a general and scalable protocol to prepare robust, highly crystalline imine COFs, based on an unexpected framework reconstruction. In contrast to standard approaches in which monomers are initially randomly aligned, our method involves the pre-organization of monomers using a reversible and removable covalent tether, followed by confined polNatureReconstructed covalent organic frameworks.PMC8986529EP/N004884/1EP/P034497/1Yu MLiu LJiang SSprick RSLittle MAZhu XWWei LWu YAn SWu XYang HZhao CTian HChen LZhang YBZhu WHBai YCooper AIZhang WZhu MMa CDai SChong SYZhu QXu YfalseReconstructed covalent organic frameworks.Covalent organic frameworks (COFs) are distinguished from other organic polymers by their crystallinity^1-3, but it remains challenging to obtain robust, highly crystalline COFs because the framework-forming reactions are poorly reversible^4,5. More reversible chemistry can improve crystallinity^6-9, but this typically yields COFs with poor physicochemical stability and limited application scope⁵. Here we report a general and scalable protocol to prepare robust, highly crystalline imine COFs, based on an unexpected framework reconstruction. In contrast to standard approaches in which monomers are initially randomly aligned, our method involves the pre-organization of monomers using a reversible and removable covalent tether, followed by confined pol2022-01-01T00:00:00Z2022 Apr2026-03-16T08:02:15.635Z2025-04-21T16:51:18.188ZS-EPMC89865293538819610.1038/s41586-022-04443-4