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Updated: Oct 29, 2025

Author Spotlight: Functionalizing Metal-Organic Frameworks: Advancements, Challenges, and the Power of Post-Synthetic Ligand Exchange
Published on: June 23, 2023
Snapshots of Postsynthetic Modification in a Layered Metal-Organic Framework: Isometric Linker Exchange and Adaptive
Weimin Lin1, Erlong Ning1, Lingyi Yang1
1Department of Chemistry, Collaborative Innovation Center of Chemistry for Energy Materials, and Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Fudan University, Shanghai 200433, P. R. China.
Abstract:
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.
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