Efficient Catalytic Oxidative Desulfurization toward Thioether and Sulfur Mustard Stimulant by Polyoxomolybdate–Resorcin[4]arene-Based Metal–Organic Materials

The design and synthesis of effective and recyclable oxidative desulfurization catalysts is of great importance in view of environmental protection and human health. Herein, a family of polyoxomolybdate-based inorganic–organic hybrid materials, namely, [Mn(TMR4A)(H2O)4][Mo6O19]·0.5CH3CH2OH·H2O (1), [Ni(TMR4A)(H2O)4][Mo6O19]·0.5CH3CH2OH·H2O (2), [Zn(TMR4A)(H2O)4][Mo6O19]·0.5CH3CH2OH·H2O (3), and [Co2(TMR4A)2(H2O)4(β-Mo8O26)]·CH3CN·12H2O (4), were assembled by the functionalized resorcin[4]arene ligand (TMR4A) with polyoxomolybdate and metal ions under solvothermal conditions. In isostructural 1–3, the [M(TMR4A)(H2O)4]2+species (M = MnII, NiII, ZnII) and [Mo6O19]2–anions are held together via C–H···O hydrogen bonds to give a 3D supramolecular architecture. In 4, two [Co(TMR4A)(H2O)2]2+cations were linked by one [β-Mo8O26]4–anion to produce an attractive molecular dimer. Remarkably, 1–4, as recyclable heterogeneous catalysts, exhibit efficient catalytic oxidation desulfurization activities toward thioethers. Particularly, 1, as a representative example, features selective catalytic oxidation for sulfur mustard simulant. Moreover, their electrochemical properties were also studied.