Hepta-Zr-Incorporated Polyoxometalate Assembly.

Driven by the synergistic-directing effect of the lacunary fragments, [B-α-GeW ₉ O ₃₄ ] ^10- and [B-α-GeW ₁₁ O ₃₉ ] ^8- , an unprecedented hepta-Zr-substituted polyoxometalate (POM) assembly K ₂ Na ₆ H ₁₀ (Hpy) ₃ [SbZr ₇ O ₆ (OH) ₄ (B-α-GeW ₉ O ₃₄ ) ₂ (B-α-GeW ₁₁ O ₃₉ ) ₂ ]·28H ₂ O ( 1 ) was made under hydrothermal condition and structurally characterized. Of which, a unique hepta-Zr cluster, [SbZr ₇ O ₆ (OH) ₄ ] ¹⁵⁺ core, was built by two trilacunary [B-α-GeW ₉ O ₃₄ ] ^10- fragments and two monolacunary [B-α-GeW ₁₁ O ₃₉ ] ^8- fragments and further arranged in a mode of a vertical cross and formed a pseudo-tetrahedron geometry. Compound 1 features the first Zr ₇ -cluster-substituted POM. Moreover, 1 is an effective heterogeneous catalyst for the catalytic oxidation of sulfides into the corresponding sulfones with H ₂ O ₂ , manifesting distinguished conversion, excellent yield, and desired recyclability.