Enhanced proton conductivity in azole-functionalized three-dimensional crystalline covalent organic frameworks.

ABSTRACT: Proton conduction pathways and mechanisms in covalent organic frameworks (COFs) have long been obscured by polycrystalline disorder. Here we report a solvent-free melt-phase post-synthetic modification (PSM) strategy that enables precise functionalization of three-dimensional single-crystalline COFs while preserving crystallinity. This methodology overcomes the limitations of solvent-mediated PSM by operating above the melting point of azole reagents, ensuring homogeneous pore accessibility without solvent occlusion. Applied to archetypal imine-linked COF-300, the method achieves crystallographically resolved conversion of fragile imine bonds (C = N, 1.245 Å) into robust amine linkages (C-N, 1.415 Å), concurrently covalently anchoring of proton-conductive azoles (C-N, 1.487 Å) on the COFs

SUBMITTER: Yao A 

PROVIDER: S-EPMC12855857 | biostudies-literature | 2026 Jan

REPOSITORIES: biostudies-literature