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

Proton-conducting materials play an important role as solid electrolytes in electrochemical devices for energy storage and conversion, including proton exchange membrane fuel cells. Metal–organic frameworks (MOFs), covalent-organic frameworks (COFs) and more recently hydrogen-bonded organic frameworks (HOFs) have emerged as useful crystalline platforms for proton transport that provide high conductivity and enable insight into conduction pathways. Here, we present two new HOFs with high conductivity, reaching 2 × 10−2 S cm−1 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.