Synthesis And Characterization Of Binary And Multimetallic Cu-based Transition Metal Oxo-clusters

Studies on giant metal-oxide clusters with highly-symmetrical structures are the recent research highlights on nanomaterials and bioinorganic chemistry.The understanding of its self-assembly law is still confined to molybdenum,manganese,copper and palladium clusters.In the previous study,we discussed the correlation between the number of metal nuclei and the giant wheel cluster and ball cluster,combined with the research results of these four kinds of metal-oxygen clusters.Studies on mixed-metals and mixed metal compounds are the research highlights in the subjects of chemistry and material science.However,they are usually hindered by the fact that only a few mixed-metal systems are available due to the issues of metal compatibility and characterization in solution.The argument is planned to explore a new complex mixed-metal system from the perspective of well-established polynuclear metal oxo-clusters.Based on our previous discovery of icosacopper oxo-clusters and a mixed Zn-Cu analogue,design and control of a variety of experimental parameters such as the metal composition and ratio to synthesize a series of icosanuclear mixed-metal nanospheric clusters.Also,knowledge and information about the complex self-assembly mechanism of these nanospheric clusters from experiments will be accumulated and analyzed,which can be further employed for the directed synthesis of mixed-metals and metal compounds with specific metal composition and ratio.Moreover,the electrical,optical,magnetic and catalytic properties of as-prepared and post-synthesized materials will be characterized,giving rise to polyelemental nanoprticle libraries.In this paper,the development of POM,high nuclear transition metal clusters and Multimetallic doped oxygen clusters are briefly reviewed.On these basis,two kinds of compounds were successfully synthesized by different synthetic methods,which were divided into the following two topics:(1)26 kinds of multimetallic oxo-clusters were synthesized by using metal acetate as raw material and organic amine as ligand in organic solvent.Only binary metals and quinary metals are discussed in this paper.The molecular formula is:{Cu12.59Ni7.41}(M20-1),{Cu10.23Ni9.77}(M20-2),{Cu8.70Ni11.30}(M20-3),{Cu9.01Ni10.99}(M20-4),{Cu12.37Ni7.63}(M20-5),{Cu10.49Ni9.62}(M20-6),{Cu10.38Ni9.62}(M20-7),{Cu9.99Ni10.01}(M20-8),{Cu10.77Co9.23}(M20-9),{Cu9.80Co10.20}(M20-10),{Cu9.41Co10.59}(M20-11),{Cu12.87Ni2.93Co2.88Zn1.12Mno.18}(M20-20),{Cu9.98Ni5.16Co4.35Zn0.41Mn0.10}(M20-21),{Cu9.06Ni4.93Co5.63Zno.23Mn0.15}(M20-22),{Cu9.37Ni6.01Co4.10Zn0.39Mn0.13}(M20-23),{Cu11.55Ni3.91Co3.39Zno.74Mno.44}(M20-24),{Cu10.16Ni5.12Co3.98Zn0.26Mn0.48}(M20-25)),{Cu9.68Ni4.45Co5.19Zn0.20Mn0.48}(M20-26).(2)Synthesis of Chiral multimetallic oxo-clusters with Tartaric Acid as Ligand Copper nitrate and Ferric Sulfate as Raw Materials.The molecular formula is:{K2[Cu6Fe(HCO2)4(D-H2C406)3(?3-O)2(OH)3]·7H2O}(D-Cu6Fe)(1){K2[Cu6Fe(HC02)4(L-H2C406)3(?3-O)2(OH)3]·7H2O}(L-Cu6Fe).The crystal structure was determined by single crystal diffraction,the molecular formula was determined by elemental analysis and ICP,and the compounds were characterized by X-ray photoelectron spectroscopy(XPS),X-ray powder diffraction(XRD),infrared(FT-T),thermogravimetry(TGA)and so on.The magnetic properties of the compounds were studied by measuring the variable temperature susceptibility and the magnetic intensity of the compounds.