Synthesis And Properties Of Covalently Attached Oxime Organic Borate Ester Metallic Complexes

The main content of this thesis is to introduce the design of functional metallic primitives, whose covalent bond framework is connected through B-O bond, using organic boronic acid as connection pieces.In this thesis, we synthetize two dinuclear complex-complex 1 and complex 2, which were respectively synthetized by 2,6-dimethylacy and manganese chloride, 2,6-diformyl-4-methylphenol(H3dfmp) and cobalt chloride-as coordination primitives. By synthetizing complex 1 and complex 2 with Phenylboronic acid respectively,{(C6H5)BⅢ[(dfmp)3MnⅡ2]BⅢ(C6H5)}-·HTEA+·3CH3OH(complex1a) (TEA=Triethylamine) and (C6H5)BⅢ[(dfmp)3CoⅡ2]BⅢ(C6H5)}-·HTEA+·2CH3OH (complex 2a) are achieved. By synthetizing complex 1 and complex 2 with 3-Aminophenylboronic boric acid respectively, (3-H2NC6H4)BⅢ[(dfmp)3MnⅡ2]BⅢ-(3-H2NC6H4)-HTEA+-nCH3OH(complex 1b) and (3-H2NC6H4)BⅢ[(dfmp)3CoⅡ2]BⅢ-(3-H2NC6H4)-HTEA+-nCH3OH(complex 2b) are achieved. Take the complex of 1,2-cyclohexanedione dioxime(H2dpg), cobalt chloride and the tetrafluoroborate ferric as the ligand primitive, synthetize the complex with the boronic acid to achieve (C6H5)BⅢ[(dpg)3Co]BⅢ(C6H5)(complex 3a) and (C6H5)BⅢ[(dpg)3Fe]BⅢ(C6H5) (complexes 4a). Coordinate compound 1 and 2, respectively with 1,4-benzene hypoboric acid to obtain coordination polymer 1c and coordination polymer 2c.The crystal of complex la was obtained through the evaporation of the methanol solution of complex la. The single crystal structure analysis showed that the crystal belongs to monoclinic system, C 2/c space group. The parameters of crystal:α= 25.870(5) A,b=15.104(3) A, c=28.107(6)A,α=90.00°,β=94.12(3)°,γ=90.00°, Volume=10954.2 (4) A3, Z=8, F(000)=5928, R1=0.0810, wR2=0.1912. Complex la is composed of the anionic on the ligand primitive of dinuclear MnⅡ, protonated cation of H3dfmp and solvent molecules.The crystal of complex 2a was obtained through the evaporation of the methanol solution of complex 2a. The single crystal structure analysis showed that the crystal belongs to monoclinic system, C 2/c space group. The parameters of crystal:a= 25.7027 (17) A,b=14.9757 (10) A, c=24.9609 (16) A, α=90.00°,β=100.6000 (10)°,γ=90.00°, Volume=9443.89 (11) A3, Z=8, F(000)=4304,R1,=0.0708, wR2=0.1831. Complex 2a is composed of the anionic on the ligand primitive of dinuclear CoⅡ, protonated cation of H3dfmp and solvent molecules.The crystal of complex 1b was obtained through the evaporation of the methanol solution of complex 1b. The parameters of crystal:a=16.146(2) A,b=14.578(2) A, c =22.312(3) A. α=90°,β=97.941(3)°,γ= 90°. Complex 1b is composed of the anionic on the ligand primitive of dinuclear Mn", protonated cation of H3dfmp and solvent molecules.The structure of complex 2b and 3a were confirmed through the infrared(IR), mass spectrometry(MS) and thermogravimetry(TGA).The crystal of complex 4a was obtained through the evaporation of the mixture of methanol-dichloromethane (1:1) solution. The single crystal structure analysis showed that the crystal belongs to monoclinic system, C c space group. The parameters of crystal:a=24.727 (9) A, b=27.881 (9) A, c=15.662 (7) A, a=90.00 °, β=123.418 (8)°,γ=90.00°, Volume=9012.48 (6) A3, Z=4, F (000)= 4080, R1= 0.0839, wR2= 0.1719. The body skeleton of complex 4a is obtained from reaction of a FeⅡ ions, three H2dpg ions and two benzene boronic at a ratio of 1:1:1.Coordination polymer 1c and coordination polymer 2c were characterized by infrared(IR) and the morphology of the compound was observed through high magnification scanning electron microscope(SEM).The electrochemical properties of the compounds were studied, and its redox properties have been discussed. Mainly measured by cyclic voltammetry(CV) and differential pulse method (DPV). the electron mobility can be achieved through the mutual conversion between different valence of metal ions, due to a pair of redox peaks in such compounds at the presence of metal ions. Based on mononuclear metal complexes and dual-core metal complexes, its conductive capacity are discussed. In addition, the linear relationship between maximum peak current and the square root of the scan rate and scan rate itself were studied.