The solvothermal oxidation of [MoO(OCCH)(HO)]·ZnCl has been established as a general route toward [MoO]-incorporated polyoxomolybdates (Mo-POMs). Two unprecedented family members: the first Mo-Mo-Mo nanocage cluster, Na[MoMoMoO(OH)Py]·11HO (1) and the first heterometallic hybrid, [MoMoZn(PO)(OH)Opy]·2(CHN)·3(CHN)·2HO (2) have been prepared and characterized by X-ray crystallography, elemental and DFT theoretical analyses, XPS, mass spectroscopy, cyclic voltammetry, and IR spectroscopy.

The largest [Mo@Mo20]-1 and the first [Ge@Mo16Zn0.5Ge1.5]-2 incorporating group IV metals are added to the [MoIV3]n-POMs hybrid cluster family, which allows for the first systematic investigation into their reasonable syntheses, diversified molecular and electronic structures, and their influence on the catalytic hydrogenation performance of such POM-FLPs system.