Structural and Mechanistic Differences in Mixed-Linker Zeolitic Imidazolate Framework Synthesis by Solvent Assisted Linker Exchange and de Novo Routes

Mixed-linker zeolitic imidazolate frameworks (ZIFs) are a subclass of metal–organic frameworks (MOFs) amenable to significant property tuning by altering the functional groups on the imidazolate linkers. Solvent assisted linker exchange (SALE) and de novo synthesis of mixed-linker ZIFs have been demonstrated, but the differences in structural properties–most importantly the linker distributions–and synthesis mechanisms of these two different types of hybrid ZIFs are unknown. In this work, a combination of 1 H NMR combined rotation and multiple pulse spectroscopy (CRAMPS), water adsorption, and nitrogen measurements reveal distinct differences in linker mixing between SALE and de novo ZIF-8–90 hybrids. Native-fluorescence confocal microscopy is shown to provide a direct means to visualize these differences. The effects of crystal size, temperature, and SALE duration were studied in detail, and a generalizable mechanism for SALE processes in ZIFs is proposed. The SALE process is found to follow a diffusion-limited behavior leading to core–shell morphologies. Under harsher SALE conditions, deviations from diffusion-limited behavior are found due to etching and partial dissolution of the initial ZIF-8 crystals. With the selection of appropriate reaction conditions, SALE processes appear to be capable of generating controlled core–shell ZIF structures of good morphological quality that complement the well-mixed structures obtained by de novo methods.