Clustering Six Electrons within “Dawson‐Like” Polyoxometalate: An Open Route toward Its Post‐functionalization

Abstract

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 (1H and 183W 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 WIV‐containing POMs known to date.