Quo vadis niobium? Divergent coordination behavior of early-transition metals towards MOF-5
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c9sc01553a.pdf
Description
Published version
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909.41 KB
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Checksum (MD5)
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Author(s)
Korzynski, Maciej Damian
Braglia, Luca
Borfecchia, Elisa
Lomachenko, Kirill A.
Baldansuren, Amgalanbaatar
Hendon, Christopher H.
Lamberti, Carlo
Dinca, Mircea
Date Issued
May 2019
Journal
Chemical Science
Publisher
Royal Society of Chemistry (RSC)
Citation
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)
Version
Final published version
Abstract
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.
MIT Department
Massachusetts Institute of Technology. Department of Chemistry
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Creative Commons Attribution Noncommercial 3.0 unported license
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DOI of Published Version
https://doi.org/10.1039/C9SC01553A
