【作者】 张劲祥；

【导师】 尹业高；

【作者基本信息】 汕头大学 ， 无机化学， 2008， 硕士

【摘要】 内部结构单元的特征以及单元间的相互联系很大程度上决定了配位聚合物本体的宏观性质。这种构性关系也成为配位聚合物结构和性质设计所遵循的一个原则。近年来,为了得到期望的配位聚合物结构和性质,从底朝上的设计思路正广泛地被应用于配位聚合物的合成和相关性质的研究。本论文的工作重点是以4-(4’-吡啶基)吡唑(Hppz)为配体溶剂热合成系列CuΙ金属配位聚合物,从中探讨吡唑环的侧链烷基对配位聚合物自组装的影响,以及研究其中一些相关产物的光致发光性质、热稳定性与结构的关系。在研究以铜-吡唑盐[Cu+(Pz?)]3 (Cu3)为基本构筑单元的配位聚合物荧光性质时,我们发现此类化合物有一些新颖的荧光热色现象,并对这一现象作了初步的探讨。此外,作者水热合成了系列的一维CuΙ聚合物链,通过比较相关的结构数据,发现氢键、疏水效应等超分子作用力对非配体支撑的亲铜作用有显著的影响,并对相关化合物的荧光性质进行了初步的研究。第1章重点回顾和总结了亲金属作用对多核d10金属配合物结构组装和荧光性质的影响。将亲金属作用构筑的几个经典金属簇简单分成几类:三核一价d10金属配合物分子(M3)的堆积模式及其荧光色变现象;铜碘簇,特别是Cu4I4(Py)4簇新颖的热致变色现象以及对它发光归属的指认;硫铜簇和多核的d10金属乙炔化物的结构特点及相关化合物的荧光热致变色现象。此外,结合配体的结构特征,阐述了本论文的研究内容和意义。第2章以3,5-二甲基-4-(4’-吡啶基)吡唑(Dmppz), 3,5-二乙基-4-(4’-吡啶基)吡唑(Deppz)作为配体,用溶剂热的方法合成了六个以Cu3构型为构筑单元的配位聚合物[Cu(Dmppz)]3 (1)、{[Cu(Dmppz)]3[CuCN]3}∞(2)、{[Cu(Dmppz)]3(CuI)}n (3) {[Cu(Deppz)3](CuI)}n (4)、{[Cu(Deppz)3](CuI)2}n (5)、{[Cu(Deppz)3](CuSCN)?(CH3CN)}n (6)和一个具有另类三核铜中心的配位聚合物{Cu3(Deppz)(CN)2}n。利用单晶X射线衍射表征了它们的晶体结构,并着重分析了它们分子间的亲铜作用和其它一些弱作用。通过结构分析和对比,总结了配体吡唑环上不同的烷基链在相似的合成条件下对分子的自组装影响。此外,对不同结构特点的配位聚合物在低温下的光致发光行为进行分类讨论,初步解释了其中的一些新颖的磷光热致变色现象。第3章分别以Dmppz, Deppz作为配体,在相似的水热反应条件下合成了系列低维的Cu(?)配位聚合物[Cu(Dmppz)Cl]∞(8)、[Cu(Dmppz)Br]∞(9)、[Cu(Deppz)Cl]∞(10)、[Cu(Deppz)Br]∞(11)、[Cu2(Deppz)2I2]∞(12)。单晶结构分析表明,在这些配位聚合物中,8-11是同构的一维链,而12是一个由Cu2I2单元与配体Deppz构筑的二维平面结构。在同构的四个化合物里,着重对比分析了两个相邻一维链之间的亲铜作用与N(C)-H…Cl(Br)氢键、烷基链的疏水效应等弱作用的关系。分析结果表明除了氢键的“支撑辅助”外,烷基链的疏水效应可能导致了相邻一维链间更短的Cu…Cu接触,说明这种效应相对于自身的空间排斥效应要占优势。更多还原

【Abstract】 The bulk performance of coordination polymer is mainly determined by the structural feature of inner bases and their associations. Such relationship becomes one rule that should be followed in designing the structures and properties of the coordination polymers. In the recent years, the bottom-up method was widely used in the preparation and related study of coordination compound to obtain the desired structure and property.This paper focuses on the solvothermal syntheses of series of Cu(?) metal coordination polymers with 4-(4’-pyridyl)-pyrazole(Hppz) as ligand, meanwhile probing the effect of alkyl of pyrazole on the self-assembly and studying the connection between photoluminescence, thermal stability and structure of some related compounds. When investigating the luminescent behaviors of the trinuclear copper-pyrazolate-based (Cu3) compounds, we found some novel luminescence thermochromism and gave a primary explanation upon them. Besides, the author hydrothermally synthesized a series of one-dimensional Cu(?) polymer chains, and found that supramolecular interactions, such as hydrogen bonding, hydrophobic effect etc, have an important impact on the ligand-unassisted cuprophilic interaction in comparison of mutual structural data. Also, the photoluminescence of the related compounds was characterized.In chapter 1, the influence of metallophilic interaction on the assembly and luminescence of multinuclear d10 metal complexes was introduced. Some of the classical metal clusters were briefly divided into several species: the packing modes and luminescence chromism phenomenon of trinuclear d10 metal complexes; cuprous iodine cluster, especially the novel thermochromism of Cu4I4(Py)4 cluster and the assignment of its photoemission; the structural feature of polynuclear cuprous cluster with chalcogen and acetylide ligands and their thermochromism. Further, in combination of ligand structure, the research content and significance of this paper were elucidated.In chapter 2, six Cu3-based coordination polymers, [Cu(Dmppz)]3 (1), {[Cu(Dmppz)]3[CuCN]3}∞(2), {[Cu(Dmppz)]3(CuI)}n (3), {[Cu(Deppz)3](CuI)}n (4), {[Cu(Deppz)3](CuI)2}n (5), {[Cu(Deppz)3](CuSCN)?(CH3CN)}n (6) and one coordination polymer beared different trinuclear copper centers, {Cu3(Deppz)(CN)2}n, were solvothermally synthesized by two ligands, 3,5-dimethyl-4-(4’-pyridyl)pyrazole (Dmppz) and 3,5-diethyl-4-(4’-pyridyl)pyrazole (Deppz) respectively. The structures of these compounds were characterized by single crystal X-ray diffraction, and more emphases were placed on analyzing the intermolecular cuprophilicity and other weak interactions. Through the mutual comparison of structural feature, some conclusions about the effect of the alkyl substituent on the molecular self-assembly were drawn. Furthermore, the photoluminescent behaviors under the frozen temperature were discriminatingly investigated according to the different structural features, and some crude conclusions were drawn to explain the novel phosphorescence thermochromism.In chapter 3, in the similar hydrothermal conditions, a series of low dimensional Cu(?) coordination polymers, [Cu(Dmppz)Cl]∞(8), [Cu(Dmppz)Br]∞(9), [Cu(Deppz)Cl]∞(10), [Cu(Deppz)Br]∞(11), and [Cu2(Deppz)2I2]∞(12) were obtained using these two ligands, Dmppz, Deppz respectively. X-ray diffraction analysis show that the compounds 8-11 are isostructural 1D chains, while compound 12 is 2D structure fabricated by Cu2I2 units and Deppz ligands. In the four isostructural compounds, the cooperative relationship of the cuprophilicity, N(C)-H…Cl(Br) hydrogen bonding, hydrophobic effect of alkyl substituent between two adjacent chains was studied. The comparison exhibited that except for the assistance of hydrogen bonding, hydrophobic effect led to a shorter Cu…Cu contact. The result showed that hydrophobic effect of alkyl is predominant over its repulsive effect.更多还原