Time-Resolved Spectroscopy and High-Efficiency Light-Driven Hydrogen Evolution of a {Mo S }-Containing Polyoxometalate-Based System.

Polyoxothiometalate ions (ThioPOM) are active hydrogen-evolution reaction (HER) catalysts based on modular assembly built from electrophilic clusters {MoS } and vacant polyoxotungstates. Herein, the dumbbell-like anion [{(PW O )Mo S (H O) (OH)} ] exhibits very high light-driven HER activity, while the active cores {Mo S } do not contain any exposed disulfido ligands, which were suspected to be the origin of the HER activity. Moreover, in the catalyst architecture, the two central {Mo S } cores are sandwiched by two {PW O } subunits that act as oxidant-resistant protecting groups and behave as electron-collecting units.

Supramolecular Association between γ-Cyclodextrin and Preyssler-Type Polyoxotungstate.

The development of hybrid materials based on polyoxometalates constitutes a strategy for the design of multifunctional materials. The slow evaporation of an aqueous solution of [NaPWO] in the presence of γ-Cyclodextrin (γ-CD) led to the crystallization of a KNa{[NaPWO]•(CHO)}•23HO () supramolecular compound, which was characterized by single-crystal X-ray diffraction, IR-spectroscopy, thermogravimetric and elemental analyses. Structural analysis revealed the formation of 1:1 {[NaPWO]•[γ-CD]} adduct in the solid state.