The Syntheses And Crystal Structure Of Polyoxometalate Supramolecular

Organic-inorganic hybrids containing vanadium-cluster heterpolyoxo--vanadiumnate or molybdenum-cluster have been synthesized through photo synthesis,conventional synthesis or hydrothermal synthesis.Five novel organic-inorganic hybrids have been synthesized at different conditions with different materials.Threeof them containing vanadium-cluster and the other two containing molybdenum-cluster.( 1 ) Two novel organic-inorganic hybrids [Hen]₂[H₂en][PMo₁₁^â…¥Mo^â…¤-O₄₀] .3.5H₂O(1)and [Hpy]₄[GeMo₁₂^â…¥O₄₀].2H)2O(2)(en=ethylicdiamine, py=pyridine) have been hydrothermal synthesized and characterized. A single crystal X-ray analysis revealed that compound 1 consists of a [PMo₁₁^â…¥Mo^â…¤O₄₀]^4- heteropolyanion, two [Hen] ⁺cations, a [H₂en]²⁺ cation and lattice water molecules. While the compound 2 is constructed by a [GeMo₁₂^â…¥O₄₀]^4-polyanion, four [Hpy]⁺ cations and two lattice water molecules. The title complexes both have the well-known α-Keggin structure, based on a central PO₄ (GeO₄) tetrahedron surrounded by 12 MoO₆ octahedra arrayed in four groups of three edge-shared MO₃O₁₃ octahedra. The groups of MO₃O₁₃ are linked to each other to the central PO₄ (GeO₄) tetrahedron by sharing corners.(2) {(NH₄)₉[AsV₁₂O₄₀(VO)₂}H₂O(3) have been synthesized using photo synthesis just for trying the different methods.(3) Two novel isopolyoxovanadiumnates {[Ni(H₂O)₈]₂[V₁₀O₂₈]}9H₂O (4) and {Co(H₂O)₈[V₁₀O₂₈]} 9H₂O(5) have been synthesized using conventional method. They are isomorphic.Both of them have [V₁₀O₂₈] unit and there are more water molecular in the crystal lattice.The [V₁₀O₂₈] anion is composed by ten distorted VO₆ octahedron sharing edges.In each VO₆ unit six oxygen atoms are at the vertex of the octahedron, the vanadium atom is inside the octahedron but not the geometry center. Every two the ten vanadium atoms constituted a two octahedron structureby sharing edges.The cluster anions joined togethered by counter cations and lattice water moleculars.The five new compounds have also characterd by elemental analyzes, IR spectrum and thermal analyzes.