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

Maciej D. Korzyński; Luca Braglia; Elisa Borfecchia; Kirill A. Lomachenko; Amgalanbaatar Baldansuren; Christopher H. Hendon; Carlo Lamberti; Mircea Dincǎ

doi:10.1039/c9sc01553a

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

Maciej D. Korzyński, Luca Braglia, Elisa Borfecchia, Kirill A. Lomachenko, Amgalanbaatar Baldansuren, Christopher H. Hendon, Carlo Lamberti, Mircea Dincǎ

Research output: Contribution to journal › Article › peer-review

15 Scopus citations

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 κ²-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.

Original language	English (US)
Pages (from-to)	5906-5910
Number of pages	5
Journal	Chemical Science
Volume	10
Issue number	23
DOIs	https://doi.org/10.1039/c9sc01553a
State	Published - 2019
Externally published	Yes

All Science Journal Classification (ASJC) codes

General Chemistry

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10.1039/c9sc01553a

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title = "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 κ2-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.",

author = "Korzy{\'n}ski, {Maciej D.} and Luca Braglia and Elisa Borfecchia and Lomachenko, {Kirill A.} and Amgalanbaatar Baldansuren and Hendon, {Christopher H.} and Carlo Lamberti and Mircea Dincǎ",

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year = "2019",

doi = "10.1039/c9sc01553a",

language = "English (US)",

volume = "10",

pages = "5906--5910",

journal = "Chemical Science",

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publisher = "Royal Society of Chemistry",

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T1 - Quo vadis niobium ? Divergent coordination behavior of early-transition metals towards MOF-5

AU - Korzyński, Maciej D.

AU - Braglia, Luca

AU - Borfecchia, Elisa

AU - Lomachenko, Kirill A.

AU - Baldansuren, Amgalanbaatar

AU - Hendon, Christopher H.

AU - Lamberti, Carlo

AU - Dincǎ, Mircea

PY - 2019

Y1 - 2019

N2 - 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 κ2-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.

AB - 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 κ2-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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JO - Chemical Science

JF - Chemical Science

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ER -

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

Abstract

All Science Journal Classification (ASJC) codes

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