【作者】 施少敏；

【导师】 胡宗球；

【作者基本信息】 华中师范大学 ， 无机配位化学， 2007， 硕士

【摘要】 1．本文合成了四种Schiff碱配体：分别为5-溴水杨醛-2-吡啶酰腙Schiff碱配体(H₂L1即C₁₃H₁₀N₃O₂Br)，邻氨基苯甲酸苯酯-2-吡啶酰胺配体(HL2即C₁₉H₁₄N₂O₃)，乙酰丙酮缩邻氨基苯甲酸Schiff碱配体(HL3即C₁₂H₁₃NO₃)，乙二醛缩水杨酰肼双Schiff碱配体(HL4即C₁₆H₁₄N₄O₄)。同时用前三种配体与Ni（Ⅱ）、Cu（Ⅱ）、Cd（Ⅱ）、Mn（Ⅱ）和Zn（Ⅱ）合成了18个过渡金属配合物，并获得了6个单晶。2．对所合成的配合物采用元素分析、红外光谱、紫外-可见光谱、摩尔电导、热重分析和X-单晶衍射进行了表征，配体还进行了质谱、核磁共振氢谱表征。用Gaussian03W程序对部分化合物进行了B3LYP/6-31G、MPW1PW91/6-31G和HF/6-31G水平的理论研究。3．单晶分别为配体C₁₉H₁₄N₂O₃、C₁₆H₁₄N₄O₄·2DMSO和配合物[Cu（L3）（H₂O）]·H₂O（10）、[Mn（L3）₂（py）₂（H₂O）₂]（16）、[Zn（L3）₂（py）₂（H₂O）₂]（17）、[Cd₂(C₂₀H₁₀N₂O₂Br₄)₂（DMF）₂]（18）（其中py代表吡啶，DMF代表N,N’-二甲基甲酰胺，DMSO代表二甲亚砜），晶体测定表明所有化合物分子均为中性分子，其晶体结构分析为：配体C₁₉H₁₄N₂O₃属三斜晶系，空间群为P-1，是由分子间的C-H…O氢键形成的二聚体。C₁₆H₁₄N₄O₄·2DMSO也属三斜晶系，空间群为P-1，是由分子间的氢键和π-π堆积作用形成的3D网状结构。[Mn（L3）₂（py）₂（H₂O）₂]（16）和[Zn（L3）₂（py）₂（H₂O）₂]（17）这两个配合物都是单核八面体构型，属单斜晶系，空间群为P2₁/n，虽然两个配合物的配位方式、配体、配位原子都相同，不过由于后者比前者配合物少一个分子间氢键C16-H16…O1，前者形成3D网状结构，后者则形成2D平面结构。而配合物[Cu（L3）（H₂O）]·H₂O（10）则是单核三角双锥构型，由分子间氢键形成2D平面结构，属正交晶系，空间群为Pbca。[Cd₂(C₂₀H（10）N₂O₂Br₄)₂（DMF）₂]（18）属三斜晶系，空间群P-1，通过氧原子桥联形成的双核配合物，呈变形八面体构型，分子间不存在氢键。4．性质研究：研究了Cu（Ⅱ）、Mn（Ⅱ）配合物的电化学性质；以H₂O₂为氧源研究了三个系列Mn（Ⅱ）配合物催化苯乙烯环氧化活性；研究了Schiff碱HL3及其Zn（Ⅱ）、Cd（Ⅱ）金属配合物的荧光活性。更多还原

【Abstract】 1. This thesis reports four Schiff base ligands: 5-bromosalicylaldehyde pyridylhy drazone (H₂L1 viz. C₁₃H₁₀N₃O₂Br), phenyl 2-picolinamidobenzoate (HL2 viz. C₁₉H₁₄N₂O₃), （E）-2-（4-oxopentan-2-ylideneamino）benzoic acid (HL3 viz. C₁₂H₁₃NO₃ ), and oxalaldehydesalicylhydrazone (HL4 viz. C₁₆H₁₄N₄O₄), respectively. And we have obtained eighteen coordination compounds of their Ni（II）, Cu（II）, Cd（II）, Mn（II） and Zn（II） complexes and six single crystals.2. All of the compounds above have been characterized by elemental analysis, infrared spectrum, ultraviolet spectroscope, molar conductivity, the thermo-gravimetric （TG） analysis and X-single crystal diffraction. The ligands were identified by hydrogen nulcear magnetic resonance and mass spectrum additionally. The full-optimized molecular geometries of the complexes were calculated at B3LYP/6-31G、MPW1PW91/6-31G and HF/6-31G levels with Gaussian03W program.3. The crystal structures of C₁₉H₁₄N₂O₃, C₁₆H₁₄N₄O₄·2DMSO, [Cu（L3） （H₂O）]·H₂O （10）,[Mn（L3）₂（py）₂（H₂O）₂]（16）,[Zn（L3）₂（py）₂（H₂O）₂]（17）,[Cd₂(C₂₀H₁₀N₂O₂Br₄)₂（DMF）₂] （18） （py=pyridine, DMF=N,N’-dimethylformamide, DMSO=dimethylsulfoxide） have been determined by X-ray diffraction. These complexes are all neutral, the crystal analysis as follows:In the title compound, C₁₉H₁₄N₂O₃, belongs to triclinic crystal system with space group P-1, and the molecules are linked by C-H…O hydrogen bonds, forming R₂¹⁰dimers which are arranged parallel to the a axis. The crystal structure of C₁₆H₁₄N₄O₄·2DMSO belongs to triclinic crystal system with space group P-1, which are connected to 3D framework structure by hydrogen bonds andπ-πinteractions. The crystal structures of [Mn（L3）₂（py）₂（H₂O）₂]（16） and [Zn（L3）₂（py）₂（H₂O）₂]（17） belong to monoclinic crystal system with space group P2₁/n; both are single nucleus and octahedron configuration; all are nearly same, such as ligand, coordinated way and ligand atoms, but hydrogen bonds of the latter are less than the former, the former are connected to 3D framework structure and the latter are connected to 2D plane by hydrogen bonds. But the crystal structure of [Cu（L3）（H₂O）]·H₂O（10） belongs to Orthorhombic crystal system with space group Pbca, and single nuclear triangle configuration, which are connected to 2D plane structure by hydrogen bonds. The crystal structure of [Cd₂(C₂₀H₁₀N₂O₂Br₄)₂（DMF）₂]（18） belongs to triclinic crystal system with space group P-1,and is octahedrally linked by oxygen atom. But there are no intramolecular hydrogen bonds. 4. Character research: the electrochemical activities of copper and manganese complexes has been studied; Epoxidation of styrene catalyzed by some manganese complexes of the three ligands as model compounds of oxygenase has been studied; HL3, their zinc and cadmium complexes has been studied更多还原