【作者】 姚小强；

【导师】 宋玉民；

【作者基本信息】 西北师范大学 ， 无机化学， 2008， 硕士

【摘要】 本论文包括四部分内容:一、绪论部分;二、以高对称性的三角架配体合成了二个Mo(W)/S/Cu金属原子簇化合物,并对其结构进行了表征;三、碘化亚铜和2,4,6-tris(pyrazole-1-yl)-1,3,5-s-triazine(tpzt)反应得到Cu(I)的一个配位聚合物,并对其结构进行了一些表征;四、合成了一个甜菜碱的稀士配合物,并对其结构进行了表征。一、绪论部分:介绍了本论文的研究背景及有关此领域的当前研究现状。二、配位聚合物大多是通过金属离子和各种有机配体反应而得到的,在这些配位聚合物中,以金属离子为节点,有机配体为桥,形成了一维链状、二维层状、三维网状等多种多样的结构,而以簇合物为节点的配位聚合物较少。一些研究小组开始尝试由簇合物取代金属离子,由于簇合物含有多个金属离子,易形成刚性的结构。Mo(W)-Cu(Ag)-S原子簇化合物由于其多变的结构,特别是由于其优良的三阶非线性光学性质而备受瞩目,大多数原子簇聚合物是以单体形式存在,而以原子簇单体为节点,以有机配体为桥联配体的的原子簇聚合物比较少见。在系统研究原子簇化合物和三阶非线性光学性质的关系的过程中,我们发现聚合物效应有可能增强其三阶非线性光学性质。以往基于异核含硫簇合物构成的超分子化合物大多数是通过低对称性的桥联配体连接起来的,例如:本课题组以4,4’-联吡啶为桥联配体得到一个三维阴阳离子穿插的类金刚烷结构的原子簇聚合物。通过高对称性的三角架配体构成的簇合物较少,有机配体对称性的改变可能会产生不同于低对称性有机配体构筑的原子簇聚合物。我们以三角架配体2,4,6-三咪唑-1,3,5-三嗪(timtz)为桥联配体,合成了2个结构新颖的三维网状结构的原子簇聚合物。三、合成了一个以三角架配体2,4,6-tris(pyrazole-1-yl)-1,3,5-s-triazine(tpzt)为桥联配体的亚铜配位聚合物,并对其进行了结构表征。四、甜菜碱(betaine)广泛存在于动植物的组织中,在有机物质中占有很重要的地位,它被用来作为氨基酸合成的甲基转化剂,是生物系统中复杂的类脂物的主要成分,它的衍生物吡啶甜菜碱(pyridine betaine, C5H5N+CH2COO-,简称pybet)存在着一个自由的羧基和一个水溶性胺基,其结构和性质已引起有关学者的兴趣,本文用吡啶甜菜碱作为配体,合成一个钕离子和甜菜碱为配体的单核配合物[Nd(pyBET)4·4H2O](ClO4)3,并对其进行了结构表征。更多还原

【Abstract】 This dissertation consists of four parts: The first chapter prolegomenon about this paper background and the current status of the research. Secondly, the synthesis, crystal structure of the tripod ligand-based three-dimensional cluster polymer; Thirdly, The reaction of 2,4,6-tris(pyrazole-1-yl)-1,3,5-s-triazine(tptz) with copper(I) halide in DMF gave a polymeric Cu (I) complex [Cu2I2(tptz)]n, The last, the crystal structure of tetrakis (pyridinioacetate) neodymium(III) tetra-hydrate perchlorate [Nd(pyBET)4·4H2O](ClO4)3.Most of coordination polymers were synthesized by self-assembly using single metal ions as nodes and suitable multi-dentate bridging ligands as linkers, to form 1D infinite chains, 2D sheet structure and 3D frameworks. Coordination polymers consisting of cluster as nodes are still rare. A number of research groups have tried to use metal cluster substitute metal ion. For the metal clusters have multiple metal sites available than single metal ion, also could form more rigid frameworks. The Mo(W)-Cu(Ag)-S clusters have been developed for their versatile structures and excellent NLO properties. Most of clusters are monomeric heterothiometallates, however, the cluster coordination polymers which the monomeric heterothiometallates were choose as knots, organic bridged ligands as spacers were rare. We have been undertaken the research of the third-order nonlinear properties of Mo(W)-Cu(Ag)-S cluster, recently, it was found that polymerization could provide an enhancement of optical limiting effects. However, to the best of our knowledge, most cluster based supramolecular compounds are connected by the low symmetrical bridging ligand, for example, our group employed monomeric Mo(W)-Cu-S clusters as building blocks and organic bridged 4,4’-bipyridines ligands as linkers yield a rare three-dimensional interpenetration nets formed from interpenetration cationic and anionic diamondoid cluster coordination polymers. In some cases, the ligand symmetry effects seem to play significant roles in the formation of discrete cluster-supported supramolecules with specific architectures. Two tripod ligand– based three-dimensional cluster polymer [WS4Cu6Br4(timtz)8/3(H2O)12]n and [MoS4Cu6I4(timtz)8/3(H2O)12]n was successfully synthesized by traditional and solvent hydrothermal methods respectively. A Cu (I) coordination polymer has been synthesized utilizing a tripod ligand-2,4,6-tris(pyrazole-1-yl)-1,3,5-s-triazine(tptz) as bridged ligand and has been characterized by elemental analysis, IR, XRD, TG and its structure was established by single crystal X-Ray diffraction.Betaines are structurally analogous to thecorresponding carboxylate anions. It is noted that a simple carboxylate can function as either bidentate chelate or bidentate bridge and tridentate bridge. Betaine and its derivatives having structure analogous to the amino acids, which can take a zwitterionic form containing positively charged quaternary ammonium and carboxylate moieties, can form stable and soluble complexes with various transition metals as extensively reported by Chen and Mak. The overall charge of neutrality of betaines enables metal—betaine complexes to bear additional anionic ligands and the stoichiometric ratio can be variously affected by steric limitation.更多还原