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

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(W^VI₂Mo^VIO₁₀)(W^VI₃O₁₀)₃]^4- in aqueous solution leads to the six-electron-reduced derivative [Si(W^IV₂Mo^IVO₇(H₂O)₃)(W^VI₃O₁₀)₃]^4- (notated SiWMo-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 SiWMo-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 SiWMo-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.