Quo vadis niobium? Divergent coordination behavior of early-transition metals towards MOF-5
Author(s)Korzynski, Maciej Damian; Braglia, Luca; Borfecchia, Elisa; Lomachenko, Kirill A.; Baldansuren, Amgalanbaatar; Hendon, Christopher H.; Lamberti, Carlo; Dinca, Mircea; ... Show more Show less
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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.
Royal Society of Chemistry (RSC)
Korzyński, Maciej D. et al. "Quo vadis niobium? Divergent coordination behavior of early-transition metals towards MOF-5." Chemical Science 23, 10 (May 2019): no. 5906 doi 10.1039/C9SC01553A ©2019 Author(s)
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