An unprecedented fully reduced {Mo(V)(60)} polyoxometalate: from an all-inorganic molecular light-absorber model to improved photoelectronic performance

Fully reduced polyoxometalates are predicted to give rise to a broad and strong absorption spectrum, suitable energy levels, and unparalleled electronic and optical properties. However, they are not available to date. Here, an unprecedented fully reduced polyoxomolybdate cluster, namely Na(8)[Mo(V)(60)O(140)(OH)(28)]·19H(2)O {Mo(V)(60)}, was successfully designed and obtained under hydrothermal conditions, which is rare and is the largest fully reduced polyoxometalate reported so far. The Mo(V)(60) molecule describes one Keggin {ε-Mo(12)} encapsulated in an unprecedented {Mo(24)} cage, giving rise to a double truncated tetrahedron quasi-nesting architecture, which is further face-capped by another four {Mo(6)} tripods. Its crystalline stability in air, solvent tolerance, and photosensitivity were all shown. As a cheap and robust molecular light-absorber model possessing wide light absorption, Mo(V)(60) was applied to build a co-sensitized solar cell photoelectronic device along with N719 dyes and the optimal power conversion efficiency was 28% higher than that of single-dye sensitization. These results show that Mo(V)(60) polyoxometalate could serve as an ideal model for the design and synthesis of all-inorganic molecular light-absorbers for other light-driven processes in the future.