Quo vadis niobium? Divergent coordination behavior of early-transition metals towards MOF-5
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 al...
| Main Authors: | , , , , , , , |
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| Other Authors: | |
| Format: | Article |
| Language: | English |
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Royal Society of Chemistry (RSC)
2020
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| Online Access: | https://hdl.handle.net/1721.1/126242 |
| _version_ | 1811079541003649024 |
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| author | Korzynski, Maciej Damian Braglia, Luca Borfecchia, Elisa Lomachenko, Kirill A. Baldansuren, Amgalanbaatar Hendon, Christopher H. Lamberti, Carlo Dinca, Mircea |
| author2 | Massachusetts Institute of Technology. Department of Chemistry |
| author_facet | Massachusetts Institute of Technology. Department of Chemistry Korzynski, Maciej Damian Braglia, Luca Borfecchia, Elisa Lomachenko, Kirill A. Baldansuren, Amgalanbaatar Hendon, Christopher H. Lamberti, Carlo Dinca, Mircea |
| author_sort | Korzynski, Maciej Damian |
| collection | MIT |
| description | 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. |
| first_indexed | 2024-09-23T11:16:42Z |
| format | Article |
| id | mit-1721.1/126242 |
| institution | Massachusetts Institute of Technology |
| language | English |
| last_indexed | 2024-09-23T11:16:42Z |
| publishDate | 2020 |
| publisher | Royal Society of Chemistry (RSC) |
| record_format | dspace |
| spelling | mit-1721.1/1262422024-06-25T18:46:33Z Quo vadis niobium? Divergent coordination behavior of early-transition metals towards MOF-5 Korzynski, Maciej Damian Braglia, Luca Borfecchia, Elisa Lomachenko, Kirill A. Baldansuren, Amgalanbaatar Hendon, Christopher H. Lamberti, Carlo Dinca, Mircea Massachusetts Institute of Technology. Department of Chemistry 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. National Science Foundation (Grant DMR-1452612) 2020-07-17T19:05:24Z 2020-07-17T19:05:24Z 2019-05 2019-03 2019-12-17T15:02:44Z Article http://purl.org/eprint/type/JournalArticle 2041-6539 https://hdl.handle.net/1721.1/126242 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) en 10.1039/C9SC01553A Chemical Science Creative Commons Attribution Noncommercial 3.0 unported license https://creativecommons.org/licenses/by-nc/3.0/ application/pdf Royal Society of Chemistry (RSC) Royal Society of Chemistry (RSC) |
| spellingShingle | Korzynski, Maciej Damian Braglia, Luca Borfecchia, Elisa Lomachenko, Kirill A. Baldansuren, Amgalanbaatar Hendon, Christopher H. Lamberti, Carlo Dinca, Mircea Quo vadis niobium? Divergent coordination behavior of early-transition metals towards MOF-5 |
| title | Quo vadis niobium? Divergent coordination behavior of early-transition metals towards MOF-5 |
| title_full | Quo vadis niobium? Divergent coordination behavior of early-transition metals towards MOF-5 |
| title_fullStr | Quo vadis niobium? Divergent coordination behavior of early-transition metals towards MOF-5 |
| title_full_unstemmed | Quo vadis niobium? Divergent coordination behavior of early-transition metals towards MOF-5 |
| title_short | Quo vadis niobium? Divergent coordination behavior of early-transition metals towards MOF-5 |
| title_sort | quo vadis niobium divergent coordination behavior of early transition metals towards mof 5 |
| url | https://hdl.handle.net/1721.1/126242 |
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