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Coupled reaction equilibria enable the light-driven formation of metal-functionalized molecular vanadium oxides
The introduction of metal sites into molecular metal oxides, so-called polyoxometalates, is key for tuning their structure and reactivity. The complex mechanisms which govern metal-functionalization of polyoxometalates are still poorly understood. Here, we report a coupled set of light-dependent and...
Autores principales: | , , , , , , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
Nature Publishing Group UK
2023
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10492840/ https://www.ncbi.nlm.nih.gov/pubmed/37689696 http://dx.doi.org/10.1038/s41467-023-41257-y |
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author | Repp, Stefan Remmers, Moritz Rein, Alexandra Stefanie Jessica Sorsche, Dieter Gao, Dandan Anjass, Montaha Mondeshki, Mihail Carrella, Luca M. Rentschler, Eva Streb, Carsten |
author_facet | Repp, Stefan Remmers, Moritz Rein, Alexandra Stefanie Jessica Sorsche, Dieter Gao, Dandan Anjass, Montaha Mondeshki, Mihail Carrella, Luca M. Rentschler, Eva Streb, Carsten |
author_sort | Repp, Stefan |
collection | PubMed |
description | The introduction of metal sites into molecular metal oxides, so-called polyoxometalates, is key for tuning their structure and reactivity. The complex mechanisms which govern metal-functionalization of polyoxometalates are still poorly understood. Here, we report a coupled set of light-dependent and light-independent reaction equilibria controlling the mono- and di-metal-functionalization of a prototype molecular vanadium oxide cluster. Comprehensive mechanistic analyses show that coordination of a Mg(2+) ion to the species {(NMe(2)H(2))(2)[V(V)(12)O(32)Cl]}(3-) results in formation of the mono-functionalized {(NMe(2)H(2))[(MgCl)V(V)(12)O(32)Cl]}(3-) with simultaneous release of a NMe(2)H(2)(+) placeholder cation. Irradiation of this species with visible light results in one-electron reduction of the vanadate, exchange of the second NMe(2)H(2)(+) with Mg(2+), and formation/crystallization of the di-metal-functionalized [(MgCl)(2)V(IV)V(V)(11)O(32)Cl](4-). Mechanistic studies show how stimuli such as light or competing cations affect the coupled equilibria. Transfer of this synthetic concept to other metal cations is also demonstrated, highlighting the versatility of the approach. |
format | Online Article Text |
id | pubmed-10492840 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2023 |
publisher | Nature Publishing Group UK |
record_format | MEDLINE/PubMed |
spelling | pubmed-104928402023-09-11 Coupled reaction equilibria enable the light-driven formation of metal-functionalized molecular vanadium oxides Repp, Stefan Remmers, Moritz Rein, Alexandra Stefanie Jessica Sorsche, Dieter Gao, Dandan Anjass, Montaha Mondeshki, Mihail Carrella, Luca M. Rentschler, Eva Streb, Carsten Nat Commun Article The introduction of metal sites into molecular metal oxides, so-called polyoxometalates, is key for tuning their structure and reactivity. The complex mechanisms which govern metal-functionalization of polyoxometalates are still poorly understood. Here, we report a coupled set of light-dependent and light-independent reaction equilibria controlling the mono- and di-metal-functionalization of a prototype molecular vanadium oxide cluster. Comprehensive mechanistic analyses show that coordination of a Mg(2+) ion to the species {(NMe(2)H(2))(2)[V(V)(12)O(32)Cl]}(3-) results in formation of the mono-functionalized {(NMe(2)H(2))[(MgCl)V(V)(12)O(32)Cl]}(3-) with simultaneous release of a NMe(2)H(2)(+) placeholder cation. Irradiation of this species with visible light results in one-electron reduction of the vanadate, exchange of the second NMe(2)H(2)(+) with Mg(2+), and formation/crystallization of the di-metal-functionalized [(MgCl)(2)V(IV)V(V)(11)O(32)Cl](4-). Mechanistic studies show how stimuli such as light or competing cations affect the coupled equilibria. Transfer of this synthetic concept to other metal cations is also demonstrated, highlighting the versatility of the approach. Nature Publishing Group UK 2023-09-09 /pmc/articles/PMC10492840/ /pubmed/37689696 http://dx.doi.org/10.1038/s41467-023-41257-y Text en © The Author(s) 2023 https://creativecommons.org/licenses/by/4.0/Open Access This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons licence, and indicate if changes were made. The images or other third party material in this article are included in the article’s Creative Commons licence, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons licence and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this licence, visit http://creativecommons.org/licenses/by/4.0/ (https://creativecommons.org/licenses/by/4.0/) . |
spellingShingle | Article Repp, Stefan Remmers, Moritz Rein, Alexandra Stefanie Jessica Sorsche, Dieter Gao, Dandan Anjass, Montaha Mondeshki, Mihail Carrella, Luca M. Rentschler, Eva Streb, Carsten Coupled reaction equilibria enable the light-driven formation of metal-functionalized molecular vanadium oxides |
title | Coupled reaction equilibria enable the light-driven formation of metal-functionalized molecular vanadium oxides |
title_full | Coupled reaction equilibria enable the light-driven formation of metal-functionalized molecular vanadium oxides |
title_fullStr | Coupled reaction equilibria enable the light-driven formation of metal-functionalized molecular vanadium oxides |
title_full_unstemmed | Coupled reaction equilibria enable the light-driven formation of metal-functionalized molecular vanadium oxides |
title_short | Coupled reaction equilibria enable the light-driven formation of metal-functionalized molecular vanadium oxides |
title_sort | coupled reaction equilibria enable the light-driven formation of metal-functionalized molecular vanadium oxides |
topic | Article |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10492840/ https://www.ncbi.nlm.nih.gov/pubmed/37689696 http://dx.doi.org/10.1038/s41467-023-41257-y |
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