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.