| Summary: | Treatment of MOF-5 with NbCl[subscript 4](THF)[subscript 2] in acetonitrile leads to incorporation of Nb(iv) centers in a fashion that diverges from the established cation metathesis reactivity of this iconic material. A combination of X-ray absorption spectroscopy analysis and reactivity studies altogether supported by density functional theory computational studies document an unprecedented binding mode for the Zn[subscript 4]O(O[subscript 2]C-)[subscript 6] secondary building units (SBUs), which in Nb(iv)-MOF-5 function as κ[superscript 2]-chelating ligands for NbCl[subscript 4] moieties, with no exchange of Zn[subscript 2]+ observed. This unusual reactivity expands the portfolio of post-synthetic modification techniques available for MOFs, exemplified here by MOF-5, and underscores the diverse coordination environments offered by this and potentially other MOFs towards heterometal species.
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