The Study Of Novel Polyoxometalates Decorated And Linked By Copper-Organonitrogen Compounds

The aim of this thesis is the synthesis of new polyoxometalate compounds on the basis of [Mo₈O₂6] ⁴, saturated Keggin and Dawson-type polyoxoanion clusters, which are decorated or bridged by various copper-organonitrogen compounds. The study on synthetic conditions and rules for these new compounds are also carried out.Eleven new polyoxometalate compounds have been synthesized on the basis of hydrothermal technique and structurally characterized by elemental analyses, IR, EPR, TG, CV and single crystal X-ray diffractions.1．Three new polyoxometalate compounds on the basis of [Mo₈O₂₆ ]⁴ polyoxoanion cluster have been hydrothermally synthesized and structurally characterized:K[{Cu^â… (2,2'-bipy)}(4,4'-bipy){Cu^â… (2,2'-bipy)}_0．5 ][Mo₈O₂₆ ](l)(H₃O)[Cu(4,4'-bipy)]₃[Mo₈O₂₆ ](2)[Cu₃^â… Cl(4,4'-bipy)₄] [Cu^â…¡(1,10-phen)₂Mo₈O₂₆ ] (3)Compound 1 exhibits copper-organonitrogen compound bisupporting polyoxometalate cluster structure. Compound 2 shows a 1D structure. Compound 3 exhibits an unprecedented 3D copper-halide 4,4'-bipy framework templated by a 1D organic-inorganic hybrid polyoxometalate chain, and it represents the first example that a 1D organic-inorganic hybrid polyoxometalate chain functions as a novel anionic template for the construction of 3D framework.2．Five new polyoxometalate compounds on the basis of saturated Keggin-type polyoxoanion cluster have been hydrothermally synthesized and structurally characterized:[Cu₅Cl(4,4'-bipy)₅] [SiW₁₂ O₄₀ ]·1．5H₂O(4)[Cu^â… (4,4'-bipy)]₃[PMo₁₂ O₁₀ ]·en·3H₂O(5)[Cu^â… (2,2'-bipy)(4,4'-bipy)_0．5 ]₂[Cu(4,4'-bipy)]₂[SiW₁₂ O₄₀ ](6)[Cu^â… ₃(4,4'-bipy)₃] [PMo₁₀ ^â…¥Mo₂â…¤O₄₀ {Cuâ…¡(2,2'-bipy)}](7)[Cu^â… (2,2'-bipy)(4,4'-bipy)_0．5 ]₂[Cuâ… (4,4'-bipy)]₂[PW₁₂ O₄₀ ]·0．25H₂O(8)The novelty of compound 4 consists in that it is the first time that saturated Keggin-type polyoxoanions are covalently linked by trinuclear Cu(â… ) complex into a 3D structure. Compound 5 is constructed from [PMo₁₂ O₄₀ ]^3-and {Cu(4,4'-bipy)}_nⁿ⁺ chain into 1D chailike structure. Compounds 6, 7 and 8 exhibit multidimensional structures formed by Keggin-type polyoxoanions and copper-organonitrogen compounds with mixed 4,4'-bipy and 2,2'-bipy ligands. To our best knowledge, compound 7 represents the first 2D structure containing the divalent copper capped polyoxometalate building blocks, which crystallized in a chiral space group P2₁． 2．Three new polyoxometalate compounds on the basis of saturated Dawson-type polyoxoanion cluster have been hydrothermally synthesized and structurally characterized:[Cuâ…¡(en)(2,2'-bipy)]₃[P₂W₁₈ O₆₂ ]·3H₂O(9)(NH₄) ₃(4,4'-H₂bipy)[Cu(4,4'-bipy)]₇[P₂W₁₈ O₆₂ ]₂·10H₂O(10)[Cu^â… (2,2'-bipy)(4,4'-bipy)_0．5 ]₂[Cu^â… (2,2'bipy)(4,4'-Hbipy)][Cu^â… (4,4'-bipy)]₂[P₂W₁₈ O₆₂ ]·3 H₂O(11)。Compound 9 exhibits copper-organonitrogen compound trisupporting polyoxometalate cluster structure with mixed 2,2'-bipy and en lignds. To our knowledge it is rare that the transition-metal complexes are supported in the same W₃O₁₃ triplet. The novelty of compound 10 consists in that it is the first time that saturated Dawson-type polyoxoanions are covalently linked by transitional metal compound into a 2D structure, and compound 11 shows a novel 1D ladderlike chain composed of saturated Dawson-type polyoxoanions and copper-organonitrogen compounds with mixed 4,4'-bipy and 2,2'-bipy ligands.