Coupled reaction equilibria enable the light-driven formation of metal-functionalized molecular vanadium oxides

Stefan Repp, Moritz Remmers, Alexandra Stefanie Jessica Rein, Dieter Sorsche, Dandan Gao, Montaha Anjass, Mihail Mondeshki, Luca M. Carrella, Eva Rentschler and Carsten Streb ()
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Stefan Repp: Ulm University
Moritz Remmers: Johannes Gutenberg University Mainz
Alexandra Stefanie Jessica Rein: Ulm University
Dieter Sorsche: Ulm University
Dandan Gao: Johannes Gutenberg University Mainz
Montaha Anjass: Ulm University
Mihail Mondeshki: Johannes Gutenberg University Mainz
Luca M. Carrella: Johannes Gutenberg University Mainz
Eva Rentschler: Johannes Gutenberg University Mainz
Carsten Streb: Ulm University

Nature Communications, 2023, vol. 14, issue 1, 1-7

Abstract: 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: 2023
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DOI: 10.1038/s41467-023-41257-y

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