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Issue 6, 2012
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Lattice-imposed geometry in metal–organic frameworks: lacunary Zn4O clusters in MOF-5 serve as tripodal chelating ligands for Ni2+

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Abstract

The inorganic clusters in metal–organic frameworks can be used to trap metal ions in coordination geometries that are difficult to achieve in molecular chemistry. We illustrate this concept by using the well-known basic carboxylate clusters in Zn4O(1,4-benzenedicarboxylate)3 (MOF-5) as tripodal chelating ligands that enforce an unusual pseudo-tetrahedral oxygen ligand field around Ni2+. The new Ni-based MOF-5 analogue is characterized by porosity measurements and a suite of electronic structure spectroscopies. Classical ligand field analysis of the Ni2+ ion isolated in MOF-5 classifies the Zn3O(carboxylate)6 “tripodal ligand” as an unusual, stronger field ligand than halides and other oxygen donor ligands. These results may inspire the widespread usage of MOFs as chelating ligands for stabilizing site-isolated metal ions in future reactivity and electronic structure studies.

Graphical abstract: Lattice-imposed geometry in metal–organic frameworks: lacunary Zn4O clusters in MOF-5 serve as tripodal chelating ligands for Ni2+

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Publication details

The article was received on 11 Mar 2012, accepted on 04 Apr 2012 and first published on 04 Apr 2012


Article type: Edge Article
DOI: 10.1039/C2SC20306E
Citation: Chem. Sci., 2012,3, 2110-2113
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    Lattice-imposed geometry in metal–organic frameworks: lacunary Zn4O clusters in MOF-5 serve as tripodal chelating ligands for Ni2+

    C. K. Brozek and M. Dincă, Chem. Sci., 2012, 3, 2110
    DOI: 10.1039/C2SC20306E

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