Authors:	Repp, Stefan Remmers, Moritz Rein, Alexandra Stefanie Jessica Sorsche, Dieter Gao, Dandan Anjass, Montaha Mondeshki, Mihail Carrella, Luca M. Rentschler, Eva Streb, Carsten
Title:	Coupled reaction equilibria enable the light-driven formation of metal-functionalized molecular vanadium oxides
Online publication date:	29-Nov-2023
Year of first publication:	2023
Language:	english
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.
DDC:	540 Chemie 540 Chemistry and allied sciences
Institution:	Johannes Gutenberg-Universität Mainz
Department:	FB 09 Chemie, Pharmazie u. Geowissensch.
Place:	Mainz
ROR:	https://ror.org/023b0x485
DOI:	http://doi.org/10.25358/openscience-9720
Version:	Published version
Publication type:	Zeitschriftenaufsatz
Document type specification:	Scientific article
License:	CC BY
Information on rights of use:	https://creativecommons.org/licenses/by/4.0/
Journal:	Nature Communications 14
Pages or article number:	5563
Publisher:	Springer Nature
Publisher place:	London
Issue date:	2023
ISSN:	2041-1723
Publisher DOI:	10.1038/s41467-023-41257-y
Appears in collections:	DFG-491381577-G