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Updated: Nov 1, 2025
Author Spotlight: Functionalizing Metal-Organic Frameworks: Advancements, Challenges, and the Power of Post-Synthetic Ligand Exchange
Published on: June 23, 2023
Single-Crystal-to-Single-Crystal Transformations of Metal-Organic-Framework-Supported, Site-Isolated Trigonal-Planar
Ricardo A Peralta1, Michael T Huxley1, Jorge Albalad1
1Centre for Advanced Nanomaterials and Department of Chemistry, The University of Adelaide, North Terrace, Adelaide, South Australia 5000, Australia.
Abstract:
Transition-metal complexes bearing labile ligands can be difficult to isolate and study in solution because of unwanted dinucleation or ligand substitution reactions. Metal-organic frameworks (MOFs) provide a unique matrix that allows site isolation and stabilization of well-defined transition-metal complexes that may be of importance as moieties for gas adsorption or catalysis. Herein we report the development of an in situ anion metathesis strategy that facilitates the postsynthetic modification of Cu(I) complexes appended to a porous, crystalline MOF. By exchange of coordinated chloride for weakly coordinating anions in the presence of carbon monoxide (CO) or ethylene, a series of labile MOF-appended Cu(I) complexes featuring CO or ethylene ligands are prepared and structurally characterized using X-ray crystallography. These complexes have an uncommon trigonal planar geometry because of the absence of coordinating solvents. The porous host framework allows small and moderately sized molecules to access the isolated Cu(I) sites and displace the "place-holder" CO ligand, mirroring the ligand-exchange processes involved in Cu-centered catalysis.
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