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杂环类金属配合物及手性席夫碱配合物的合成、结构及表征
【作者】 曹赞；
【作者基本信息】 江西理工大学 ， 化学工艺， 2010， 硕士
【摘要】 本论文以过渡金属离子和稀土金属离子为配位离子,设计并合成了九个含联吡啶羧基配体的多核金属配合物、四唑金属配合物、手性席夫碱多核金属配合物、氰基桥联的金属配合物,解析了其单晶结构,并对部分配合物进行了光谱、热稳定性等方面的研究。1.利用2, 2’-联吡啶-3, 3’-二羧酸-1, 1’-二氧化物[（R, S）-H2BDCD]和CuCl2·2H2O （或Ba（NO3）2·6H2O）进行反应,生成两个新颖的三维配位聚合物{[Cu（BDCD）2]·H2O}n, 1和[Ba（BDCD）2·2H2O]n, 2。晶体结构测定表明化合物1中有多种纳米笼结构,化合物2是一个新颖的双核结构。2.通过水热反应,在水和乙醇中合成杂金属聚合物{[Nd2Cu2（L）2 （OXA）4·2（2H2O）]·2（3H2O）}n,3和{[EuCu（bpdc）2·4（H2O）I)]·2H2O}n, 4.晶体结构测定表明,配合物3是一个具有新颖的拓扑结构的化合物。Nd离子配位几何构型为九配位变形的三棱柱结构。Cu离子配位几何构型为五配位变形的四方锥结构。所有的2, 2’-联吡啶-3-羧酸以四配位的方式与不同的Cu原子和一个Nd原子相连接,从而在c-轴方向形成梯状结构。草酸按配位方式可分为两类,一部分以四配位的方式与不同的Cu原子和Nd原子形成两个五元环;另一部分以四配位的方式与不同的Nd原子结合形成两个五元环。配合物4通过Eu3+和羧基沿a轴方向形成一维链状结构,通过Cu2+和配体中的N原子沿b轴方向形成二维网状结构。3.将氟虫腈、叠氮化钠和CuCl2（或Cd（ClO4）2）溶入水和乙醇中反应,合成了化合物5,[Cu （L）2]（H2O）2]·2H2O和化合物6,[Cd （L）2]（H2O）2]·2H2O。晶体结构测定表明化合物5和6中的两种金属都与两个水分子、两个来自不同四唑基中的N原子和两个吡唑基中的N原子结合,构成六配位模式。Cu2+离子和Cd离子的配位几何构型为变形的八面体。在化合物5中,四唑和两个参与配位的水分子形成双重旋转轴。在这两个化合物中存在许多氢键和弱的π-π共轭作用,这有助于化合物自身的稳定组装。4.利用2,6-二甲酞基-4-甲基苯酚和（R）-2-氨基丁醇形成的schiff碱,与Cu2+反应,合成了化合物7,[Cu（MBD）2（N3）6]和化合物8,[Cu （MBD） Cl4],晶体结构测定表明,化合物7是一个六核铜簇合物,而化合物8是一个双核铜。2,6-二甲酞基-4-甲基苯酚缩脂肪胺作为多齿配体通过酚羟基氧原子和醇羟基氧原子及亚胺氮原子与铜原子配位。化合物7中,Cu原子有两种配位方式:五配位和四配位。5.将环己二胺, Cu（ClO4）2 ,[BuN]3[Fe（CN）6]进行反应,合成了化合物{2Cu （DMCL）2·[Fe（CN）6]}n·2H2O, 9.晶体结构测定表明,配合物中存在μ4桥联和μ2桥联两种桥联模式。四桥联连接的四个Cu离子在同一平面内,赤道相邻氰基氮原子桥联的两个配体平面几乎是垂直的。μ2桥联模式和μ4模式中的对位氰基氮原子桥联的两个配体平面几乎是平行的。6.分析分子间作用力、配体构型、配位模式、辅助配体对于整个结构的影响,探索合成产物的结构特征和化学物理性能间的关系。
【Abstract】 A total of nine new complexes have been designed and synthesized by using transition and rare earth metal ions as coordinated center, with pyridine carboxyl, tetrazole, Schiff base and cyanometallic anions as bridged ligands. Their crystal structures were determined by X-ray single crystal diffractometer, and some properties of those complexes have been characterized by IR, TG-DTA and spectrofluorophotometer.1. Utilizing 2, 2’-bipyridine-3, 3’-dicarboxylic acid 1, 1’-dioxide [（R, S）-H2BDCD] and CuCl2·2H2O （or Ba（NO3）2·6H2O） under hydrothermal condition produce two novel three dimensional coordination polymers {[Cu（BDCD）2]·H2O}n, 1 and [Ba（BDCD）2·2H2O] n, 2. X-Ray Crystallography Measurements reveals that compound 1 contain many kinds of interesting nano-cavities,and compound 2 exhibits a novel binuclear Ba2+ core.2. Obtained two 3d-4f heterometallic polymeric complex {[Nd2Cu2（L）2 （OXA）4·2（2H2O）]·2（3H2O）}n,3 and {[EuCu（bpdc）2·4（H2O）I)]·2H2O}n, 4 from hydrothermal reaction in the presence of ethanol and water. X-ray single crystal diffraction investigation of the polymeric complexes {[Nd2Cu2 （L）2（OXA）4·2（2H2O）]·2（3H2O）}n,3 exhibits an interesting and novel topological structure. The local coordination environments around the Nd center can be best described as a slightly distorted three face centered trigonal prism which is connected by six oxygen atoms from three different oxalate ligands through monodentate coordination modes, one oxygen atom from the carboxylic group of 2, 2’-bipyridine-3-cayboxylate ligand and double water molecules. Another metal center Cu1 adopts a slightly distorted square pyramidal coordination mode, in which the square plane was defined by double oxygen atoms from different carboxylate groups of the same oxalate liagnd, double nitrogen atoms from 2, 2’-bipyridine-3-cayboxylate. All the 2, 2’-bipyridine-3-cayboxylate ligands acting as tetradentate ligands link double different Cu atoms and one Nd atom, thus resulting in the formation of a 1D ladder-like structure along the c-axis. Interestingly, the oxalate ligands can be classified as two types according to the coordination modes of carboxylate. Part of them as tetradentate ligands link different Cu and Nd atoms through forming double five-member rings, and others as tetradentate ligands link different Nd atoms also through forming double five-member rings. Single-crystal X-ray diffraction analysis reveals that complex {[EuCu（bpdc）2·4（H2O）I)]·2H2O}n, 4 is interconnected by Eu3+ through carboxylic groups to produce a linear 1D structure along a direction, then through Cu2+ chelating double nitrogens of bpdc2- ligand along b direction to form the 2D Cu2+-Eu3+ heterometallic-organic framework.3. Heat treatment （refluxing） a mixture of fipronil, sodium azide and CuCl2 in the mixed solvent of ethanol and water gave complex 4, [Cu（L）2]（H2O）2]·2H2O. Hydrothermal reaction of fipronil, sodium azide and Cd（ClO4）2 in the presence of water and ethanol （Demko-Sharpless tetrazole synthesis methods） yields complex 5, [Cd（L）2]（H2O）2]·2H2O. X-Ray Crystallography Measurements reveals that the center metals in both complexes are six coordinated which connected by two water molecules, two nitrogen atoms from different tetrazolyl groups and two nitrogen atoms from pyrazolyl groups respectively. So the central metal atom in both the complexs adopts a distorted octahedral coordination mode. In complex 4, CuII lies on a two fold rotation axis made up of double tetrazole ligands and two coordinated water molecules. Interestingly, many different hydrogen bonds and weak supramolecular interactions involvesπ-πstacking can be found in both compounds, important in supramolecular assembly and stabilization of the compounds.4. Utilizing Cu2+ and the Schiff base derived from 2,6-dimethylphenyl-4-methylphenol and 2-Aminobutanol produce two coordination clusters [Cu（MBD）2（N3）6], 6 and [Cu（MBD）Cl4], 7. X-Ray Crystallography Measurements reveals that compound 6 contains unusual six nuclear and compound 7 exhibits a binuclear Cu2+ core. Schiff base derived from 2,6-dimethylphenyl-4-methylphenol and 2-amine-1-butanol acting as polydentate ligand by phenolichydroxyl oxygen atoms, alcoholichydroxyl oxygen atoms and nitrogen atom coordinates to copper atoms. In compound 6, there are two kinds of coordination modes around Cu center: five coordinated and four coordinated.5. {2Cu （DMCL）2·[Fe（CN）6]}n·2H2O was synthesized by the reaction of 1,2-Diaminocyclohexane, Cu（ClO4）2 and [BuN]3[Fe（CN）6]. X-Ray Crystallography Measurements reveals that it contains two bridgingspaces:μ4 bridging mode andμ2 bridging mode. the four Cu which coordinated to the same [Fe（CN）6]3- lie in the same plane, and the two planes of ligands connecting to the adjacent cyanide is nearly vertical. But the planes of ligands connecting to the para-position cyanide are almost parallel, as well as in 2-bridging mode.6. Explored the impact of intermolecalar force, auxiliary ligand, molecular configuration and coordination model of ligand on the entire structure of the coordination complexes and the relationship between structural feature and chemical physical properties of the products.