Synthesis, Structure And Properties Of Complexes Based On Oxime And N-heterocycle Ligands

The synthesis, structures, magnetic properties and catalytic properties of transitionmetal complexes based on oxime and N-heterocycle ligands were reported in this thesis.Twenty coordination complexes were obtained by using solvothermal method. Theluminescent properties, magnetic properties and the catalytic activities of somecomplexes were investigated. The results were briefly described as follows.1. By employing N-hydroxy-pyridine-2-carboxamidine (H2pyoax) as the ligand,six coordination complexes of compositions，[Cd{(py)C(NH2)NOH}2Cl2](1),[Co(OMe)2{(py)C(NH2)NOH}2]·2(CH3CH2OH)(2),[Zn2(O2CMe)3{(py)C{(py)C(NH2)NOH}4](OH)(3),[Zn4(OH)2{(py)C(NH2)NO}4Cl2]·3MeCN (4),[Ni(SO4)(H2O){(py)C(NH2)NOH}2]·H2O (5)， and [Mn(SO4){(py)C(NH2)NOH}2]n(6) weresynthesized by using different metal salts, adjusting the solvents, and tuning the pHvalues of the system.The photoluminescent property of complex4was studied. Complex6is the firstcoordination polymer of manganese (II) supported by the pyridine-2-amidoxime ligand.Variable temperature (2.0–300K) magnetic studies for the linear chain complex6indicate weak antiferromagnetic MnII MnIIexchange interactions.2. Nine complexes of formulas [Co(HPIPM)Cl2]n(7),[Cu2(MPIP)2Cl4](8),[Cu(MPIP)Br2](9),[Zn(MPIP)Cl2](10),[Mn(BPIPM)Cl2]·CH3OH (11),[Cr(BPIPM)Cl2]Cl·H2O (12),[Zn(EPIP)Cl2](13),[Cu2(EPIP)2Cl4](14),[Cu(EPIP)Br2](15) and [BPIPM](16)(MPIP=1-(methoxymethyl)-3-(pyridin-2-yl)imidazo[1,5-a]pyridine; BPIPM=bis(3-(pyridin-2-yl)imidazo[1,5-a]pyridin-1-yl)methane; EPIP=1-(ethoxymethyl)-3-(pyridin-2-yl)imidazo[1,5-a]pyridine) were synthesized via thereaction of (3-(pyridin-2-yl)imidazo[1,5-a]pyridin-1-yl)methanol (HPIPM) withdifferent metal salts under solvthemal conditions. The structures of complexes7-12aredifferent due to the use of different metal salts. The reaction of CoCl2with HPIPM gave a complex with a chain structure. When MnCl2and CrCl3were used as the startingmaterials, respectively, new coordination complexes based on a new ligand whichcontains a in situ generated secondary carbon atom were generated. As CuCl2，CuBr2and ZnCl2were used as the starting materials, respectively, HPIPM ligand reacted withthe solvent to produce an etherate ligand (MPIP), which coordinates with metals to givethe corresponding complexes. Complexes13-15were obtained in ethanol by usingCuCl2，CuBr2，ZnCl2as the metal salts. A new ligand16which contains a secondarycarbon atom was seperated by adding HOAc in the reaction system.The luminescent properties of complexes10and13were studied, and they allshow strong emission in solid state at room temperature. Compared with ligand, theemission wavelength of the complexes were red-shifted. Complexes8and9cancatalyze the reactions of methyl ethyl ketone and ethylene glycol ketal. By tuning theamount of the catalyst and the temperature of the reactions, good yields were obtained.3. Schiff base ligands based on pyridine-imidazo[1,5-a]pyridine derivatives, HL1,HL2, L3were designed and synthesized. Four new complexes, namely,[Co(L1)2]·CH3CH2OH·H2O (17),[Co(L2)2](18),[Ni(Cl)2L3)]n·CH3OH (19) and[Co(Cl)2L3)]n·CH3OH (20) were obtained. Complexes17and18are isostructural.Each metal center exhibits octahedron coordination environment. Complexes19and20are also isostructural, and they are all linear coordination polymers in which the metalcenters are connected by the ligands and Cl atoms.