Covalent organic frameworks have emerged as a powerful synthetic platform for installing and interconverting dedicated molecular functions on a crystalline polymeric backbone with atomic precision. Here, we present a novel strategy to directly access amine-linked covalent organic frameworks, which serve as a scaffold enabling pore-wall modification and linkage-interconversion by new synthetic methods based on Leuckart–Wallach reduction with formic acid and ammonium formate. Frameworks connected entirely by secondary amine linkages, mixed amine/imine bonds, and partially formylated amine linkages are obtained in a single step from imine-linked frameworks or directly from corresponding linkers in a one-pot crystallization-reduction approach. The new, 2D amine-linked covalent organic frameworks, rPI-3-COF, rTTI-COF, and rPy1P-COF, are obtained with high crystallinity and large surface areas. Secondary amines, installed as reactive sites on the pore wall, enable further postsynthetic functionalization to access tailored covalent organic frameworks, with increased hydrolytic stability, as potential heterogeneous catalysts.
This dataset contains all data from analytical measurements including FT-IR spectra, calculated IR modes, raw XRD patterns, 1H, 13C, 15N and 1H/13C-HETCOR ssNMR spectra, N2 sorption isotherms, pore-size distributions, BET plots, SEM and TEM images, SEM-EDX spectra, quantum-chemically optimized structures, calculated NMR chemical shifts, reduced total scattering patterns, PDF analysis and Rietveld structure refinements of the journal article mentioned under the related publication.
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