Synthesis,Structure,Magnetic And Density Functional Theory Calculation Of Ru-Ru Metal Bond Compounds

In recent years,the development of metal bond chemistry is becoming rapidly,there are more than a thousand kinds of compounds that have been reported,this paper mainly study in two-core ruthenium metal bond compounds.For now,the reports about Ru2(hedp)23-,Ru2(OAc)4+,Ru2(CO3)43-,Ru2(PO4)47 and etc that are used as building templates and other ions assembled to form compounds has already a lot,except for Ru2(OAc)4+,most of these reports are limited to the introduction of the compounds of crystal structure,spectroscopy,magnetic properties and etc,besides,in-depth study for the properties of the electronic structure,metal bonding,electron transition of the compound cannot be directly measured from experimental instruments.As the development of computational chemistry,the combination of theoretical calculation and experient has become a major trend in modern chemistry and it's also the necessary means to solve the problems.In this paper,based on the synthesis of crystal structures of the dinuclear ruthenium metal bond compounds,using Gaussian09 to calculate the compounds by density functional theory(DFT),we have obtained electronic structure,metal bonds,UV spectra,electron transitions,front molecular orbital of these conpounds and thus one step closer to understand the properties of these compounds.The main results include four aspects:1.Synthesis of the Crystal Structure and Density Functional Theory Calculation of the Ru2?/?(PO4)2L2n-(L=H2O,Cl,Br)CompoundsAt room temperature,mixed valence state of K7Ru2?/?(PO4)4(H2O)2 add two drops H2O2,turning into the same valence state of K7Ru2?/?(PO4)4(H2O)2.(1)CH5N3·HNO3 was added to this solution,and thus aquired a two-dimensional layered compound H2(CN3H6)4[Ru2(PO4)4(H2O)2].Besides,to replace H2O in the axial position with halogen ion,(2)add CH5N3 HNO3 and LiCl to this solution to obtain a two-dimensional layered compound H4(CN3H6)4[Ru2(PO4)4Cl2].(3)Adding CH5N3·HNO3 and LiBr into this solution to get a two-dimensional layered compound H4(CN3H6)4[Ru2(PO4)4Br2].Measure magnetism and conduct DFT calculations of the model compounds of[Ru2(PO4)4X2]n-.2.Density Functional Theory Study of the Ru2(HPO4)4(H2O)2n-(n=3 and 2)with different valence states(Ru2?/? and Ru2?/?)To compare with the electronic structure,metal bonds,UV spectra,electron transitions,front molecular orbital of different valence states(Ru2?/? and Ru2?/?)of the Ru2(HPO4)4(H2O)2n-(n=3and 2),we have found that central metal bond unit Ru25+has the electronic structure ?2?4?*2?*1,S=3/2,that is,two ?*and ?*three orbital spin degeneration,the metal bond order is 2.5.And the central metal bond unit Ru26+has the electronic structure S=2;?,two ?*and ?*four orbital spin degeneration,the metal bond order is 2.3.Study on the Magnetic Properties and Density Functional Theory of the Ru2?/?(CO3)4(H2O)23-K1/3[Ni(H2O)6]4/3[Ru2(CO3)4](H2O)2]·2H20 was prepared by adding Ni2+into the mixed valence state Ru2?/?(CO3)43-aqueous solution at a low temperature.The magnetic properties of the compound demonstrate that the compound is an antiferromagnetic compound.And then DFT calculations were performed on the molecular orbital,metal metal bond,UV spectrum and spin density of the compound.4.Density Functional Theory Study on Ru2(hedp)2X2n-(X=H2O,Cl,Br)After the compounds of Ru2(hedp)2X2n-(X=H2O,Cl,Br)were synthesized,their electronic structure,metal bond and UV spectra were different due to the different positions of the ligands in the axial position.It is found that the UV spectrum is red shifted from H2O to Br by the density functional theory calculation.The result is consistent with the experimental results.