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Article Dans Une Revue Inorganic Chemistry Année : 2023

Making Heterometallic Metal-Metal Bonds in Keggin-Type Polyoxometalates by a Six-Electron Reduction Process

Résumé

Polyoxometalates (POMs) represent a promising class of molecular electron reservoirs. However, their multielectron reduction gives rise to intricate physical-chemical phenomena that must be fully understood for their future use in energy-storage devices. Herein, we show that bulk electrolysis of the archetypal Keggin-type POM [Si(WVI2MoVIO10)(WVI3O10)3]4- in aqueous solution leads to the six-electron-reduced derivative [Si(WIV2MoIVO7(H2O)3)(WVI3O10)3]4- (notated SiW11Mo-VI′) in which the mixed-metal triad acts as a storage unit for six electrons and six protons. X-ray diffraction analysis and multinuclear NMR (183W and 95Mo) studies reveal that this electron-rich species represents the first example of POMs containing heterometallic metal-metal bonds between addenda centers. This electron-rich POM can be further reduced through multielectronic events, while its full oxidation restores the structure of the oxidized parent ion. Remarkably, the formation of SiW11Mo-VI′ results from a fast clustering process compared to that observed for the entirely W-based analogue, revealing that the formation of metal-metal bonds in the mixed-metal Mo/W POM is facilitated because the reaction rate is not limited by a slow disproportionation step. Last, we evaluate the supramolecular properties of SiW11Mo-VI′ using a method based on the cloud-point measurement of a nonionic surfactant. This investigation demonstrates that the clustering process has dramatic consequences on the solution behavior of the POM, canceling its superchaotropic character due to a local structuring effect of the hydration shell. These fundamental results pave the way for applications using the massive electron-storage properties of mixed-metal POMs.

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Chimie
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hal-04122776 , version 1 (19-10-2023)

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Clément Falaise, Gabrielle Mpacko Priso, Nathalie Leclerc, Mohamed Haouas, Emmanuel Cadot. Making Heterometallic Metal-Metal Bonds in Keggin-Type Polyoxometalates by a Six-Electron Reduction Process. Inorganic Chemistry, 2023, 62 (6), pp.2494-2502. ⟨10.1021/acs.inorgchem.2c03769⟩. ⟨hal-04122776⟩
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