Coupled reaction equilibria enable the light-driven formation of metal-functionalized molecular vanadium oxides
- Publikationstyp:
- Zeitschriftenaufsatz
- Metadaten:
-
- Autoren
- Stefan Repp
- Moritz Remmers
- Alexandra Stefanie Jessica Rein
- Dieter Sorsche
- Dandan Gao
- Montaha Anjass
- Mihail Mondeshki
- Luca M Carrella
- Eva Rentschler
- Carsten Streb
- Autoren-URL
- https://www.webofscience.com/api/gateway?GWVersion=2&SrcApp=fis-test-1&SrcAuth=WosAPI&KeyUT=WOS:001066679400012&DestLinkType=FullRecord&DestApp=WOS_CPL
- DOI
- 10.1038/s41467-023-41257-y
- eISSN
- 2041-1723
- Externe Identifier
- Clarivate Analytics Document Solution ID: R8GF8
- PubMed Identifier: 37689696
- Ausgabe der Veröffentlichung
- 1
- Zeitschrift
- NATURE COMMUNICATIONS
- Artikelnummer
- ARTN 5563
- Datum der Veröffentlichung
- 2023
- Status
- Published
- Titel
- Coupled reaction equilibria enable the light-driven formation of metal-functionalized molecular vanadium oxides
- Sub types
- Article
- Ausgabe der Zeitschrift
- 14
Datenquelle: Web of Science (Lite)
- Andere Metadatenquellen:
-
- Abstract
- <jats:title>Abstract</jats:title><jats:p>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<jats:sup>2+</jats:sup> ion to the species {(NMe<jats:sub>2</jats:sub>H<jats:sub>2</jats:sub>)<jats:sub>2</jats:sub>[V<jats:sup>V</jats:sup><jats:sub>12</jats:sub>O<jats:sub>32</jats:sub>Cl]}<jats:sup>3-</jats:sup> results in formation of the mono-functionalized {(NMe<jats:sub>2</jats:sub>H<jats:sub>2</jats:sub>)[(MgCl)V<jats:sup>V</jats:sup><jats:sub>12</jats:sub>O<jats:sub>32</jats:sub>Cl]}<jats:sup>3-</jats:sup> with simultaneous release of a NMe<jats:sub>2</jats:sub>H<jats:sub>2</jats:sub><jats:sup>+</jats:sup> placeholder cation. Irradiation of this species with visible light results in one-electron reduction of the vanadate, exchange of the second NMe<jats:sub>2</jats:sub>H<jats:sub>2</jats:sub><jats:sup>+</jats:sup> with Mg<jats:sup>2+</jats:sup>, and formation/crystallization of the di-metal-functionalized [(MgCl)<jats:sub>2</jats:sub>V<jats:sup>IV</jats:sup>V<jats:sup>V</jats:sup><jats:sub>11</jats:sub>O<jats:sub>32</jats:sub>Cl]<jats:sup>4-</jats:sup>. 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.</jats:p>
- Autoren
- Stefan Repp
- Moritz Remmers
- Alexandra Stefanie Jessica Rein
- Dieter Sorsche
- Dandan Gao
- Montaha Anjass
- Mihail Mondeshki
- Luca M Carrella
- Eva Rentschler
- Carsten Streb
- DOI
- 10.1038/s41467-023-41257-y
- eISSN
- 2041-1723
- Ausgabe der Veröffentlichung
- 1
- Zeitschrift
- Nature Communications
- Sprache
- en
- Artikelnummer
- 5563
- Online publication date
- 2023
- Status
- Published online
- Herausgeber
- Springer Science and Business Media LLC
- Herausgeber URL
- http://dx.doi.org/10.1038/s41467-023-41257-y
- Datum der Datenerfassung
- 2023
- Titel
- Coupled reaction equilibria enable the light-driven formation of metal-functionalized molecular vanadium oxides
- Ausgabe der Zeitschrift
- 14
Datenquelle: Crossref
- Abstract
- 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<sup>2+</sup> ion to the species {(NMe<sub>2</sub>H<sub>2</sub>)<sub>2</sub>[V<sup>V</sup><sub>12</sub>O<sub>32</sub>Cl]}<sup>3-</sup> results in formation of the mono-functionalized {(NMe<sub>2</sub>H<sub>2</sub>)[(MgCl)V<sup>V</sup><sub>12</sub>O<sub>32</sub>Cl]}<sup>3-</sup> with simultaneous release of a NMe<sub>2</sub>H<sub>2</sub><sup>+</sup> placeholder cation. Irradiation of this species with visible light results in one-electron reduction of the vanadate, exchange of the second NMe<sub>2</sub>H<sub>2</sub><sup>+</sup> with Mg<sup>2+</sup>, and formation/crystallization of the di-metal-functionalized [(MgCl)<sub>2</sub>V<sup>IV</sup>V<sup>V</sup><sub>11</sub>O<sub>32</sub>Cl]<sup>4-</sup>. 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.
- Addresses
- Institute of Inorganic Chemistry I, Ulm University, Albert-Einstein-Allee 11, 89081, Ulm, Germany.
- Autoren
- Stefan Repp
- Moritz Remmers
- Alexandra Stefanie Jessica Rein
- Dieter Sorsche
- Dandan Gao
- Montaha Anjass
- Mihail Mondeshki
- Luca M Carrella
- Eva Rentschler
- Carsten Streb
- DOI
- 10.1038/s41467-023-41257-y
- eISSN
- 2041-1723
- Externe Identifier
- PubMed Identifier: 37689696
- PubMed Central ID: PMC10492840
- Funding acknowledgements
- European Research Council: 101002212
- Deutsche Forschungsgemeinschaft (German Research Foundation): 389183496
- Ministeriums für Wissenschaft, Weiterbildung und Kultur (Ministerium für Wissenschaft, Weiterbildung und Kultur Rheinland-Pfalz): SusInnoScience
- Deutsche Forschungsgemeinschaft (German Research Foundation): 390874152
- Deutsche Forschungsgemeinschaft (German Research Foundation): 404530119
- Deutsche Forschungsgemeinschaft (German Research Foundation): 510966757
- Gutenberg Forschungskolleg (Gutenberg Research College): n.a.
- Open access
- true
- ISSN
- 2041-1723
- Ausgabe der Veröffentlichung
- 1
- Zeitschrift
- Nature communications
- Sprache
- eng
- Medium
- Electronic
- Online publication date
- 2023
- Open access status
- Open Access
- Paginierung
- 5563
- Datum der Veröffentlichung
- 2023
- Status
- Published
- Publisher licence
- CC BY
- Datum der Datenerfassung
- 2023
- Titel
- Coupled reaction equilibria enable the light-driven formation of metal-functionalized molecular vanadium oxides.
- Sub types
- research-article
- Journal Article
- Ausgabe der Zeitschrift
- 14
Files
https://europepmc.org/articles/PMC10492840?pdf=render
Datenquelle: Europe PubMed Central
- Abstract
- 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 Mg2+ ion to the species {(NMe2H2)2[VV12O32Cl]}3- results in formation of the mono-functionalized {(NMe2H2)[(MgCl)VV12O32Cl]}3- with simultaneous release of a NMe2H2+ placeholder cation. Irradiation of this species with visible light results in one-electron reduction of the vanadate, exchange of the second NMe2H2+ with Mg2+, and formation/crystallization of the di-metal-functionalized [(MgCl)2VIVVV11O32Cl]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.
- Date of acceptance
- 2023
- Autoren
- Stefan Repp
- Moritz Remmers
- Alexandra Stefanie Jessica Rein
- Dieter Sorsche
- Dandan Gao
- Montaha Anjass
- Mihail Mondeshki
- Luca M Carrella
- Eva Rentschler
- Carsten Streb
- Autoren-URL
- https://www.ncbi.nlm.nih.gov/pubmed/37689696
- DOI
- 10.1038/s41467-023-41257-y
- eISSN
- 2041-1723
- Externe Identifier
- PubMed Central ID: PMC10492840
- Funding acknowledgements
- Deutsche Forschungsgemeinschaft (German Research Foundation): 390874152
- Deutsche Forschungsgemeinschaft (German Research Foundation): 389183496
- Deutsche Forschungsgemeinschaft (German Research Foundation): 510966757
- Deutsche Forschungsgemeinschaft (German Research Foundation): 404530119
- Deutsche Forschungsgemeinschaft (German Research Foundation): 510966757
- Deutsche Forschungsgemeinschaft (German Research Foundation): 390874152
- EC | EU Framework Programme for Research and Innovation H2020 | H2020 Priority Excellent Science | H2020 European Research Council (H2020 Excellent Science - European Research Council): 101002212
- Ministeriums für Wissenschaft, Weiterbildung und Kultur (Ministerium für Wissenschaft, Weiterbildung und Kultur Rheinland-Pfalz): SusInnoScience
- Gutenberg Forschungskolleg (Gutenberg Research College): n.a.
- Ausgabe der Veröffentlichung
- 1
- Zeitschrift
- Nat Commun
- Sprache
- eng
- Country
- England
- Paginierung
- 5563
- PII
- 10.1038/s41467-023-41257-y
- Datum der Veröffentlichung
- 2023
- Status
- Published online
- Titel
- Coupled reaction equilibria enable the light-driven formation of metal-functionalized molecular vanadium oxides.
- Sub types
- Journal Article
- Ausgabe der Zeitschrift
- 14
Datenquelle: PubMed
- Author's licence
- CC-BY
- Autoren
- Stefan Repp
- Moritz Remmers
- Alexandra Stefanie Jessica Rein
- Dieter Sorsche
- Dandan Gao
- Montaha Anjass
- Mihail Mondeshki
- Luca M Carrella
- Eva Rentschler
- Carsten Streb
- Hosting institution
- Universitätsbibliothek Mainz
- Sammlungen
- DFG-491381577-G
- Resource version
- Published version
- DOI
- 10.1038/s41467-023-41257-y
- File(s) embargoed
- false
- Open access
- true
- ISSN
- 2041-1723
- Zeitschrift
- Nature Communications
- Schlüsselwörter
- 540 Chemie
- 540 Chemistry and allied sciences
- Sprache
- eng
- Open access status
- Open Access
- Paginierung
- 5563
- Datum der Veröffentlichung
- 2023
- Public URL
- https://openscience.ub.uni-mainz.de/handle/20.500.12030/9738
- Herausgeber
- Springer Nature
- Datum der Datenerfassung
- 2023
- Datum, an dem der Datensatz öffentlich gemacht wurde
- 2023
- Zugang
- Public
- Titel
- Coupled reaction equilibria enable the light-driven formation of metal-functionalized molecular vanadium oxides
- Ausgabe der Zeitschrift
- 14
Files
coupled_reaction_equilibria_e-20231129153630204.pdf
Datenquelle: OPENSCIENCE.UB
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