An unprecedented nanocage-like and heterometallic [MoIV3O4]-polyoxomolybdate hybrid

The solvothermal oxidation of [Mo₃O₂(O₂CCH₃)₆(H₂O)₃]·ZnCl₄ has been established as a general route toward [Mo⁴⁺₃O₄]-incorporated polyoxomolybdates (Mo^IV-POMs). Two unprecedented family members: the first Mo⁴⁺-Mo⁵⁺-Mo⁶⁺ nanocage cluster, Na[MoMoMoO₄₃(OH)Py₁₂]·11H₂O (1) and the first heterometallic hybrid, [MoMoZn(PO₄)₄(OH)₂O₃₁py₃]·2(C₅H₆N)·3(C₅H₅N)·2H₂O (2) have been prepared and characterized by X-ray crystallography, elemental and DFT theoretical analyses, XPS, mass spectroscopy, cyclic voltammetry, and IR spectroscopy.