We report a postsynthetic strategy and its implementation to make covalent organic frameworks (COFs) with irreversible hydrazide linkages. This involved the synthesis of three 2D and 3D hydrazine-linked frameworks and their oxidation. The linkage synthesis and functional group transformation—hydrazine and hydrazide—was evidenced by 15N multi-CP-MAS NMR. In addition, the isothermal water uptake profiles of these frameworks were studied, leading to the discovery of one hydrazide-linked COF suitable for water harvesting from air in arid conditions. This COF displayed characteristic S-shaped water sorption profiles, a steep pore-filling step below 18% relative humidity at 25 °C, and a total uptake capacity of 0.45 g g-1. We found that even small changes made on the molecular level can lead to major differences in the water isotherm profiles, therefore pointing to the utility of water sorption analysis as a complementary analytical tool to study linkage transformations.
Synthesis and full characterization of COFs including EA, FT-IR spectroscopy, NMR spectra, PXRD data, computational modeling, gas uptake measurements, TGA, and water iso-therms (PDF); X-ray crystallographic data for COF-670-hydrazine (CIF)