Amine-Linked Covalent Organic Frameworks as a Platform for Postsynthetic Structure Interconversion and Pore-Wall Modification

Covalent organic frameworks have emerged as a powerful synthetic platform for installing and interconverting dedicated molecular functions on crystalline polymeric backbone with atomic precision. Here, we present novel strategy to directly access amine-linked covalent frameworks, which serve scaffold enabling pore-wall modification linkage-interconversion by new methods based Leuckart–Wallach reduction formic acid ammonium formate. Frameworks connected entirely secondary amine linkages, mixed amine/imine bonds, partially formylated linkages are obtained in single step from imine-linked or corresponding linkers one-pot crystallization-reduction approach. The new, 2D rPI-3-COF, rTTI-COF, rPy1P-COF, high crystallinity large surface areas. Secondary amines, installed reactive sites the pore wall, enable further postsynthetic functionalization tailored increased hydrolytic stability, potential heterogeneous catalysts.