Assembly of polyoxometalate-thiacalix[4]arene-based inorganic-organic hybrids as efficient catalytic oxidation desulfurization catalysts.

Self-assembly of polyoxometalates, Ni(ii)/Ag(i) cations and tetra-[5-(mercapto)-1-methyltetrazole]-thiacalix[4]arene (L) yielded three inorganic-organic hybrids, namely, [NiL(CHOH)(HO)][PMoO]·3CHOH·2HO (1), [NiL(CHOH)(HO)][PWO]·3CHOH·2HO (2) and [AgL(PMoO)] (3). In hybrids (1) and (2), Ni(ii) cations are linked by L ligands to produce layered frameworks, and H bonds among the [PMoO]/[PWO] anions and L ligands lengthen the structures to form 3D supramolecular architectures. Hybrid (3) exhibits a 3D architecture, of which Ag(i) cations not only coordinated with the N and O atoms of L ligands and [PMoO] anions simultaneously, but also connected each other by Ag-Ag interactions. It is worth mentioning that 1 and 3 as recyclable catalysts show excellent heterogeneous catalytic activity in oxidation desulfurization reactions.