The Syntheses,Characterizations And Properties Of Sphere-shaped Icosanuclear Copper-and Copper-zinc Oxo Clusters

Metal-oxo clusters are attracting more and more chemists to engage in the research of this field,which makes the metal-oxo cluster compounds to develop very quickly in recent years.Metal-oxo cluster is a significant development trend,and it is penetrating into material science and functional materials with excellent properties.Because of its charming structure and unique coordination mode of ligand,multinuclear compounds with high symmetry aroused the chemists' interests.Metal-oxo clusters have a good application in magnetic materials,catalysis,molecular recognition,gas storage and other fields.The halide ions,sulfur atom,oxygen and so on,commonly appear in bridging ligands,and mixed bridging ligands also appear in federation frequently.Nuclear number of metals range from four to a few hundred.In addition,the synthesis of metal-oxo cluster has entered into the stage of molecular tailoring and assembly.The design of molecular materials at the molecular level make the metal-oxo cluster compounds with optical,electrical,magnetic,and other physical properties possible.A summary of the development,synthesis and application of metal-oxo cluster compounds were made in this paper,and different representative of metal-oxo clusters were introduced.In Consideration of magnetic property and other unique physical properties of copper-oxo clusters,we designed and synthesized two multinuclear copper-oxo clusters,and a {Cu12Zn8} cluster was synthesized on the basis of the original structure.In this paper,the main research work can be summarized as the following:1.The reaction of Cu(OAc)2 with n-propylamine in wet acetonitrile at room temperature,followed by filtration and crystallization under slow evaporation,a new type[Cu20(OH)24(CH3COO)8(n-C3H7NH2)10CO3](CH3COO)6·15H2O(1)cluster was synthesized.Fragile crystals of 1 led us to replace the n-propylamine ligands by the sterically more congested and less toxic isopropylamines,giving rise to the more air-stable compound[Cu20(OH)24(CH3COO)6(iso-C3H7NH2)8CO3](CH3COO)8·10H2O(2).The structure and properties of the two clusters have been characterized.2.Using isopropylamine as the organic alkali,with copper acetate and zinc acetate as raw materials in acetonitrile solvent,after recrystallization processing,a new kind of 3d-3d nuclear cluster complex of {M20} family[Cu12Zn8(OH)24(CH3COO)12CO3](CH3COO)3(iso-C3H7NH2)2(iso-C3H7NH3)·12H2O was synthesized and its structure and properties have been characterized.3.In this paper,different pretreatment methods were applied.Metal-oxo cluster compounds of 2 and 3 were calcined at high temperature,the nano CuO and CuO/ZnO ball were obtained.In order to further study the influence of the ratio of copper and zinc on the properties of heterogeneous materials,solid ultraviolet diffuse reflection of the CuO,CuO/ZnO was tested.the stable structure and synthesis technique of {M20} are very important in the synthesis of other multinuclear clusters and the research of the connection between transition metal atoms.Doped with different performance and proportion of metal atoms in the metal-oxo clusters,a target multi-function metal-oxo cluster compound can be created.Metal oxides evolved from hetero-nuclear metallic complexes can control the proportion and uniformity of metal oxides better.