From non-conductive MOF to proton-conducting metal-HOFs: a new class of reversible transformations induced by solvent-free mechanochemistry

at 60 °C and 75% relative humidity, obtained in reactions that represent a new class of reversible transformations of solids. The reactions are induced by solvent-free mechanochemistry and involve breaking of coordination linkages in a MOF and formation of extended hydrogen-bonded networks of metal-HOFs (MHOFs). This unprecedented class of MOF-to-MHOF transformations has been demonstrated using a non-conductive MOF (JUK-1) and formamidinium or methylammonium thiocyanates as solid reactants. Structural details of the solid-state reactions are revealed by powder X-ray diffraction and Rietveld refinements for the MHOF products. None of the attempts using conventional methods were successful in obtaining the MHOFs, emphasizing a unique role of mechanochemical stimuli in the reactivity of supramolecular polymer solids, including crystalline MOFs and HOFs. The reversible nature of non-covalent interactions in such materials may be utilized for the development of healable polymer systems.