The Synthesis, Structure And Properties Of Molybdenum Oxygen Cluster Derivatives.

In this paper, we adopted mainly Keggin or Dawson-type ion as the basic building blocks which was linked proper ringlike organic ligand with nitrogen atom through covalent bond or molecular interaction under the hydrothermal synthesis method. There are nine new synthesized supermolecule compounds or organic-inorganic hybrid compounds by different pH and raw material,and all compounds have been structurally characterized by IR, TG, elemental analyses, X-ray single crystal diffraction and SEM. And we studies preliminarily the synthesis conditions and regularity of compounds and catalytic activity.1, Two new Wells-Dowson molybdosulfates have been synthesized via hydrothermal synthesis [C₅N₂H₁₄]₂[S₂Mo₁₈^ⅥO₆₂]·8H₂O(1) [C₅N₂H₁₄]₈(H₃O)₂[S₂Mo₂^ⅤMo₁₆^ⅥO₆₂ ]₃·(C₅H₅N)₂(2) both compounds contain full protonated N-methylpiperazine cations in compound 1, each N-methylpiperazine links two polyanions by N-H...O hydrogen bonding interactions to generate a 1D chain. The most significant aspect of compound 2 is that the polyanions are linked by protonated water (H₃O)⁺ and N-methylpiperazine cations by using hydrogen bonding interactions to form a soft 3D supermolecule framework.2, Foure new organic-inorganic hybrid compounds based on Keggin have been synthesized by inducing 4'4-bipy under hydrothermal synthesis: compound 3 appears polyanions [SiMo₁₂O₄₀]^4- which is coordinated by [{Cu(2'2-bipy)}₆Mo₆O₂₂]⁴⁺ through Mo-Ot to form a 1D chain.π-πinteractions and hydrogen bonding interactions joint the chains to emerge the 3D supermolecule framework. In compound 4, Keggin [SiMo₁₂O₄₀]^4- anions are connected through infinite cations [Cu(4'4-bipy)]⁺n chains by Cu-O to represent 2D organic-inorganic hybrid framework. Both compound 5 and 6 exhibit polyanions [SiMo₁₂O₄₀]^4- are linked to the protonated ligands by the hydrogen bonding interactions to generate 3D supermolecule framework.3, Under hydrothermal synthesis, two new compounds based on capped Keggin units have been obtained. Compound 7 and 8 reprsent the capped Keggin linked the protonated ligands by hydrogen bonding interactions to come into 3D supermolecule framework.4, A compound based on [γ-Mo₈O₂₆]^4- has been synthesized under hydrothermal synthesis: Cu₄(C₃N₂H₄)₁₀Mo₈O₂₆(H₂O)4 (9), Compound 9 exhibits a discrete [γ-Mo₈O₂₆]^4- cluster coordinated [Cu(C₃N₂H₄)₂]⁺cations, and this clusters are jointed throughπ-πinteraction and hydrogen bonding interactions to come into 3D supermolecule framework.