Carbazole-based bis-imidazole ligand-involved synthesis of inorganic–organic hybrid polyoxometalates as electrochemical sensors for detecting bromate and efficient catalysts for selective oxidation of thioether

Abstract

Considering the potential application on preparing electrode and catalyst materials of inorganic–organic hybrid polyoxometalates, a bis-imidazole ligand with carbazole as a connector, 3,6-di(1H-imidazol-1-yl)-9H-carbazole (L), was used for preparing inorganic–organic hybrid polyoxometalates. As a result, three complexes formulated by [NiL₂(Mo₂O₇)] (1), [Cu(H₂O)₂(HL)₂ (β-Mo₈O₂₆)]·H₂O (2) and [Ni₂(H₂O)₄L₂ (CrMo₆(OH)₅O₁₉)]·6H₂O (3) were obtained successfully. Structural analysis indicated that the different polyoxoanions and metal ions showed important influences on the formation of structures. In the presence of Ni²⁺ ions and heptamolybdate, a 2D network constructed from Ni²⁺ ions and L ligands was formed in complex 1, in which the [Mo₄O₁₄]⁴⁻ polyoxoanions were encapsulated. But the use of Cu²⁺ ions led to a 1D chain of complex 2, which was composed of [β-Mo₈O₂₆]⁴⁻ polyoxoanions and mononuclear {CuL₂} units. By utilizing [CrMo₆(OH)₅O₁₉]⁴⁻ as the inorganic building block, complex 3 showed a 2D (4, 4)-connected layer. Complexes 1–3 could be employed as electrode materials for sensing bromate with the limits of detection of 0.315 μM for 1, 0.098 μM for 2 and 0.551 μM for 3. Moreover, these complexes showed efficient catalytic activity for the selective oxidation of thioethers.