Synthese, Structures And Property Study Of Coordination Complexes Based On Different Metal-oxygen Clusters

The aim of this thesis is to synthesize new metal-oxygen cluster compounds on the basis of organic drugs, organic N-donor ligands and metal ions or multi-nuclear metal-oxygen clusters, to study the synthetic conditions and rules for these compounds, analysis influence of multi-nuclear metal-oxygen clusters on the formation of ultimate structures, and to explore the relationships between structures and properties for these new compounds. A series of new helical coordination compounds have been synthesized on the basis of room temperature reaction and solvothermal technique and structurally characterized by elemental analyses, IR, XRPD, TG and single crystal X-ray diffractions. The thermal stabilities and fluorescent activity of these compounds have been studied.1. Three new organotin compounds have been synthesized on the basis of azo ligand. Organooxotin clusters 1 and 2 have the common dimeric tetraorganodistannoxane skeleton; while organooxotin cluster 3 has a Sn4O2 core. In 1, compound shows an interesting 2D suppramolecular layerlike structure. [(Bu₂Sn)_<sub>2(O)(OH)(HL)]₂ (1) [(Bu₂Sn)_<sub>2(O)(OEt)(HL)]₂ (2) [Bu_<sub>2(HL)SnOSn(HL)Bu₂]₂ (3) (H₂L: (E)-2-hydroxy-4-(phenyldiazenyl)benzoic acid)2,Two unprecedented dinuclear Sn compounds containing deprotonatedβ-cyclodextrins have been constructed by using different organotin and inorganotin precursors under solvothermal condition for the first time, which displays two dinuclear airscrew-like structures with different packing modes. [Sn₂^IV(β–CD)₃]H_-8·H₂O (4) [Sn₂^IV(β–CD)₃]H_-8 (5) (β–CD =β–cyclodextrin)3,Five organic-inorganic hybrid compounds have been synthesized on the basis of different metal centers, [Mo₈O₂₆]^4- and flexible fcz ligand. Comparing these compounds, metal centers with different coordination abilities and modes can influence the ultimate structure and dimensions. [Co₂(fcz)₄Mo₈O₂₆]·9H₂O (6) [Ni₂(fcz)₄Mo₈O₂₆]·9H₂O (7) [Zn₂(fcz)₄Mo₈O₂₆]·3H₂O (8) [Cu₂(fcz)₄Mo₈O₂₆]·4H₂O (9) [Ag₄(fcz)₄Mo₈O₂₆] (10) (fcz = 1-(2,4-difluorophenyl)-1,1-bis[(1H-1,2,4-triazol-1-yl)methyl]ehanol)4,Inorganic-organic hybrid materials based on Keggin polyoxometalate building blocks combined with CuII/CuI and flexible fluconazole (Hfcz) ligand have been obtained. By carefully inspection of the structures, it is believed that various transition-metal organic units which are formed by Hfcz ligand combined with CuII/CuI cations and Keggin polyanions with different coordination modes are important for the formation of the different structures. In addition, coordination polymers are prepared by hydrothermal reaction because of their poor solubility in water and in common organic solvent. This property is very advantageous to expand the application of POM-based materials in chemically bulk-modified electrode. [Cu^II₂(Hfcz)₄(SiW₁₂O₄₀)]·3H₂O (11) [CuII4(fcz)₄(H₂O)₄(SiMo₁₂O₄₀)]·6H₂O (12) [Cu^II₂(fcz)₂][Cu^II₄(fcz)₄(SiW₁₂O₄₀)][Cu^II₂(fcz)_<sub>2(H₂O)_<sub>2(SiW₁₂O₄₀)]·6H₂O (13) (Et₃NH)₂[Cu^I₂(Hfcz)_<sub>2(SiW₁₂O₄₀)]·2H₂O (14) (Et₃NH)₂[Cu^I₂(Hfcz)_<sub>2(SiW₁₂O₄₀)]·H₂O (15) [Cu^I₄(Hfcz)₄(SiMo₁₂O₄₀)] (16)5,Four new coordination polymers with d10 metal clusters have been synthesized on the basis of 3,3',4,4'-benzophenone tetracarboxylate anion (H4BPTC) and 4,4'-oxydiphthalate (H4ODPT) with different imidazole ligands. [Zn₂(BPTC)(L¹)]·H₂O (17) [Zn_2.5(BPTC)(L²)(OH)(H₂O (18) [Zn₂(ODPT)(L³)_0.5(H₂O)]·3H₂O (19) [Cd_1.5(HODPT)(L⁴)_0.5] (20)(L¹ = 1,4-bis(imidazol-1-ylmethyl)benzene, L² = 1,4-bis(2-ethyl-imidazol-1-yl)butane,L³ = 1,2-bis[2-(2-pyridyl)imidazol-1-ylmethyl]benzene and L⁴ = 1,4-bis[2-(2-pyridyl)imidazol-1-ylmethyl]benzene)...