Synthesis, Crystal Structures And Properties Of Monovacant Keggin Heteropolymolybdates

Two unusual transition-metal-monosubstituted heteropolymolybdates have beensynthesized in aqueous solution. These compounds were structurally characterized by IR,UV-Vis, elemental analyses, TG and single crystal X-ray diffractions. The electrocatalysis, thestability of the compounds and magnetic property of the compounds have been discussed.These compounds is composed of the imidazole cations, hydration water and monovacantKeggin polyoxoanion [SiMo₁₁M（H₂O）O₃₉]6-（M=Ni,Mn）.（C₃H₅N₂）6[SiMo₁₁Ni（H₂O）O₃₉]·7H₂O （1）（C₃H₅N₂）6[SiMo₁₁Mn（H₂O）O₃₉]·8H₂O （2）One of the most attractive feature of photoxometalate is the metal-oxygen frameworkcan undergo reversible and stepwise,multielectron-transfer reaction. Their very rich redoxchemistry makes them suitable for electrode modification,electrocatalysis and electroanalysis.thus, it has great significance that the design and development of modified electrode based onPOMs, extend the application of POMs modified eletrode in electrocatalysis andphotoelectrocatalysis. In this paper, we find that the （C₃H₅N₂）6[SiMo₁₁Ni（H₂O）O₃₉]·7H₂O、（C₃H₅N₂）6[SiMo₁₁Mn（H₂O）O₃₉]·8H₂O and α-H4SiMol2O40have the electrocatalytic activity ofNO, especially, SiMol2and SiMo₁₁Ni which have excellent stability of the electrode.Moreover, we also research the interaction of POMs and CO2in the non-polar solvent.