Snapshots of Postsynthetic Modification in a Layered Metal-Organic Framework: Isometric Linker Exchange and Adaptive Linker Installation

Terminal ligand exchange and framework linker exchange have been frequently practiced as powerful tools to functionalize reticular structures such as metal-organic frameworks (MOFs). Herein, we report the postsynthetic modification (PSM) of a 6-connected layered MOF (hxl topology) to achieve a 12-connected fcu framework. In the PSM process, isometric linker exchange in the layers and linker installation between adjacent layers by the substitution of modulating ligands happen simultaneously. Snapshots of PSM at different time points reveal that the hxl domain is adaptively reorganized to create sites for new linker installation, and gradually the fcu domain dominates the crystal. Detailed kinetic analysis suggests that, although adaptive linker installation requires interlayer expansion of stackings in situ, it is kinetically faster than isometric linker exchange in the layers.

Automated summary

Terminal ligand exchange and framework linker exchange are powerful tools for functionalizing reticular structures like MOFs, with kinetic analysis showing adaptive linker installation is faster than isometric linker exchange. In this study, a 6-connected layered MOF was postsynthetically modified to achieve a 12-connected fcu framework through simultaneous isometric linker exchange and linker installation between layers. Adaptively reorganized domains create sites for new linker installation, gradually transitioning to dominate the crystal structure.