Self-assembly of a novel multicomponent polyoxometalate-based tetrahedral supercluster with high catalytic activity for thioether oxidation.

A glamorous polyoxometalate (POM)-based macromolecule containing a tetrahedral supercluster (Hbiz) 12 [(P 2 Co 2 MoV4O 8 ) 2 (P 2 MoV2O 8 ) 4 (Pb⊂P 6 Co 2 MoV2MoVI14O 73 ) 4 ]· ca. 129H 2 O (1) was in situ self-assembled from three novel components, [Pb⊂P 6 Co 2 Mo 16 O 73 ] 8- (P 6 Co 2 Mo 16 ), [P 2 MoV2O 8 ] 4+ (P 2 Mo 2 ) and [P 2 Co 2 MoV4O 8 ] 18+ (P 2 Co 2 Mo 4 ), respectively. To our knowledge, 1 represents the first tetrahedral supercluster containing the basket-like POM structure. Besides, macromolecule 1 exhibits high catalytic activity and reusability for the oxidation of thioethers to sulfoxides.