Hepta-Zr-Incorporated Polyoxometalate Assembly

Driven by the synergistic-directing effect of the lacunary fragments, [B-α-GeW₉O₃₄]^10- and [B-α-GeW₁₁O₃₉]^8-, an unprecedented hepta-Zr-substituted polyoxometalate (POM) assembly K₂Na₆H₁₀(Hpy)₃[SbZr₇O₆(OH)₄(B-α-GeW₉O₃₄)₂(B-α-GeW₁₁O₃₉)₂]·28H₂O (1) was made under hydrothermal condition and structurally characterized. Of which, a unique hepta-Zr cluster, [SbZr₇O₆(OH)₄]¹⁵⁺ core, was built by two trilacunary [B-α-GeW₉O₃₄]^10- fragments and two monolacunary [B-α-GeW₁₁O₃₉]^8- fragments and further arranged in a mode of a vertical cross and formed a pseudo-tetrahedron geometry. Compound 1 features the first Zr₇-cluster-substituted POM. Moreover, 1 is an effective heterogeneous catalyst for the catalytic oxidation of sulfides into the corresponding sulfones with H₂O₂, manifesting distinguished conversion, excellent yield, and desired recyclability.