Study On Syntheses,crystal Structures And Properties Of 3d And 3d-4f Metal Complexes And Coordination Polymers Constructed From Salamo-based Bisoximes

Salamo-based compound is a kind of multidentate ligand with unique structure and N₂O₂coordination cavity,while transition metal ions or rare earth metal ions can get mono-,bi-or polynuclear metal complexes with tetradentate chelation by coordination with N₂O₂ unique cavity of this kind of organic compound.More than a decade ago,experts and scholars at home and abroad are usually studying Salen-based compounds.Compared with Salamo-based compounds,there are less two more electronegative oxygen atoms,so Salamo-based compounds show stronger coordination ability and higher stability.In the construction of such bisoxime metal complexes,Salamo ligands and various metal cations are usually used to participate in the coordination in a certain chemical atmosphere.As a result,Salamo-based metal complexes with different physical and chemical properties,different spatial configurations and excellent practical performance can be obtained.Salamo-type compounds can self-assemble directly with metal ions to obtain homopolynuclear or heteropolynuclear complexes,or can be used multidentate nitrogen-containing ligands,polydentate carboxylic acid ligands and polydentate carboxylic acid pyridine ligands as connecting rods,using metal ions as nodes to assemble to obtain coordination polymers.These multidentate ligands can also self-assemble directly with metal ions to obtain homopolynuclear or heteropolynuclear complexes.Therefore,in recent years,scholars at home and abroad have begun to use this kind of multidentate ligands as connecting rods to connect Salamo complexes,which is also the main research direction of this thesis.In this thesis,a hexadentate Salamo-based ligand（H₂L）were used to self-assemble with transition metal ions and rare earth metal ions to synthesize eleven 3d-4f heterometallic complexes;A single-armed Salamo-based ligand（H₃L）was used to react with transition metal ions to obtain three homonuclear copper（Ⅱ）,zinc（Ⅱ）and cadmium（Ⅱ）complexes.The all synthesized ligands and complexes were characterized by elemental analyses,IR spectra,UV-Vis spectra,and the structures of the corresponding complexes were determined by X-ray single crystal diffractometer.In addition,the fluorescence properties and antibacterial activities of some complexes were temporarily carried out.The details are as follows:1.Through reaction of the Salamo-based ligand H₂L,nickel（Ⅱ）acetate,lanthanide（Ⅲ）nitrate（Ln=La,Ce,Pr,Nd,Sm,Gd and Tb）and terephthalic acid（H₂bdc）,respectively,seven 3d-4f Ni（Ⅱ）-Ln（Ⅲ）polymers were self-assembled:five two-dimensional polymers²∞[Ni（DMF）（L）Ln（bdc）_1.5]（Ln=La（1）and Nd（4））,²∞[Ni₂（DMF）₂（L）₂Ln₂（bdc）₃]·CH₃OH（Ln=Ce（2）,Pr（3）and Sm（5））,two one-dimensional polymers[Ni（L）Ln（NO₃）（DMF）（bdc）]（6,7:Gd and Tb）.2.Self-assembly of Salamo-based ligand H₂L with nickel（Ⅱ）acetate or copper（Ⅱ）acetate,lanthanide（Ⅲ）nitrate（Ln=Pr and Sm）and 4,4′-bipyridine to obtain two 3d–4f heterometallic polymers:one is a one-dimensional chain polymer¹∞[NiL（4,4?-bipy）Pr（NO₃）₃]·（CH₃）₂CHOH（8）,another is a tetranuclear dimer[{CuLSm（NO₃）)₃}₂（4,4?-bipy）]·CH₃OH（9）.By the ligand H₂L with copper（Ⅱ）acetate,lanthanide（Ⅲ）nitrate（Ln=Eu and Dy）gives two 3d–4f heterometallic copper（Ⅱ）)–Ln（Ⅲ）complexes,[{CuL（CH₃CH₂OH）Dy（NO₃）₃]（10）and[{CuL（CH₃CH₂OH）Eu（NO₃）₃]（11）.Antibacterial activity tests were performed on complexes 8,9 and 10.3.Single crystals of one ligand H₃L and three 3d transition metal complexes were obtained by the reactions of the ligand H₃L with copper（Ⅱ）acetate,zinc（Ⅱ）acetate and cadmium（Ⅱ）acetate,respectively:[Cu₂（L）（μ-OAc）]·CHCl₂（12）,[Zn₂（L）（μ-OAc）（H₂O）]·3CHCl₃（13）and[{Cd₂（L）（OAc）（CH₃CH₂OH）}₂]·2CH₃CH₂OH（14）.