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Quo vadis niobium? Divergent coordination behavior of early-transition metals towards MOF-5

Abstract

Treatment of MOF-5 with NbCl4(THF)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 Zn4O(O2C–)6 secondary building units (SBUs), which in Nb(IV)-MOF-5 function as κ^2-chelating ligands for NbCl4 moieties, with no exchange of Zn2+ 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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Publication details

The article was received on 29 Mar 2019, accepted on 07 May 2019 and first published on 09 May 2019


Article type: Edge Article
DOI: 10.1039/C9SC01553A
Chem. Sci., 2019, Accepted Manuscript
  • Open access: Creative Commons BY-NC license
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    Quo vadis niobium? Divergent coordination behavior of early-transition metals towards MOF-5

    M. D. Korzyński, L. Braglia, E. Borfecchia, K. A. Lomachenko, A. Baldansuren, C. H. Hendon, C. Lamberti and M. Dinca, Chem. Sci., 2019, Accepted Manuscript , DOI: 10.1039/C9SC01553A

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