Clustering Six Electrons within "Dawson-Like" Polyoxometalate: An Open Route toward Its Post-functionalization.

Autor: Priso GM; Institut Lavoisier de Versailles, CNRS, UVSQ, Université Paris-Saclay, 45 avenue des Etats-Unis, 78035, Versailles, France., Haouas M; Institut Lavoisier de Versailles, CNRS, UVSQ, Université Paris-Saclay, 45 avenue des Etats-Unis, 78035, Versailles, France., Leclerc N; Institut Lavoisier de Versailles, CNRS, UVSQ, Université Paris-Saclay, 45 avenue des Etats-Unis, 78035, Versailles, France., Falaise C; Institut Lavoisier de Versailles, CNRS, UVSQ, Université Paris-Saclay, 45 avenue des Etats-Unis, 78035, Versailles, France., Cadot E; Institut Lavoisier de Versailles, CNRS, UVSQ, Université Paris-Saclay, 45 avenue des Etats-Unis, 78035, Versailles, France.
Jazyk: angličtina
Zdroj: Angewandte Chemie (International ed. in English) [Angew Chem Int Ed Engl] 2023 Dec 04; Vol. 62 (49), pp. e202312457. Date of Electronic Publication: 2023 Nov 06.
DOI: 10.1002/anie.202312457
Abstrakt: Super-reduction of polyoxometalates (POMs) in solution is of fundamental interest for designing innovative energy storage systems. In this article, we show that the "Dawson-like" POM can undergo a disproportionation process during its massive electron uptake, leading to species containing three metal-metal bonds as evidenced by X-ray diffraction, multi-nuclear magnetic resonance spectroscopy ( 1 H and 183 W NMR), extended X-ray absorption fine structure (EXAFS), UV/Vis, and voltammetry techniques. This result indicates that electron storing within metal-metal bonds is not a unique property of Keggin-type POM as postulated since the 70s. Besides, we demonstrate that the presence of an electron-rich triad in the "Dawson-like" POM allows its post-functionalization with additional tungstate ions, generating a chiral molecule that is also the largest W IV -containing POMs known to date.
(© 2023 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)
Databáze: MEDLINE
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