【作者】 王福民；

【导师】 高胜利； 陈三平；

【作者基本信息】 西北大学 ， 无机化学， 2011， 博士

【摘要】 含有杂原子的多官能团羧酸刚性配体是制备异核功能金属配合物最为常见的配体之一。吡嗪羧酸是一类含有N、O多齿多功能有机配体,配位方式多种多样,能与多种金属发生配位作用,有利于形成结构新颖的异核金属配合物。在前期开展2-吡嗪甲酸配合物研究的基础上,本论文选用5-甲基-2-吡嗪甲酸作为配体,基于配合物配体策略,构筑了六个新型的3d-4f,一个3d-3d及一个4s-3d异核金属-有机骨架化合物,并进行了结构表征；在利用铜配合物配体合成异核金属配位聚合物的过程中,发现了六类产物与配合物配体之间存在着结构转化关系,并利用单晶衍射或粉末衍射实验进行确证。选用2,3-吡嗪二甲酸单酰胺为原料,在水热条件下,组装了十五个2,3-吡嗪二甲酸合稀土-铜异核金属配位聚合物,并对其结构和性能进行了探讨。具体的研究内容和研究结果如下：1)选用5-甲基-2-吡嗪甲酸(5-Methylpyrazine-2-carboxylic acid, Hmpca)镍配合物配体与硝酸银在水溶液中反应,构筑了2D波形平面镍银异核金属配位聚合物。以铜配合物配体与稀土/主族金属离子在水溶液中反应,制备了七个1D或2D有机-异核金属配位聚合物(2)～(8)。结构分析表明,配合物(2)及(3)互为异质同构体；配合物(5)～(8)互为异质同构体。用KOH调节溶液的pH,获得一个2D铜钾异核金属配合物(4),参与配位的C1-离子起着模板作用。2)在甲醇溶剂中,Hmpca与铜盐反应制备了2D配合物[Cu(mpca)2](25);[Cu(mpca)2(H2O)]·3H2O配合物配体与La(NO3)3在水溶液中制备了单核配合物[Cu(Hmpca)2(H2O)2]-2NO3·2H2O(26);在配合物配体与RECl3制备Cu-RE的过程中,用NaOH调节溶液pH得到了1D配合物{[Cu(mpca)(μ-Cl)(H2O)]·H2O}n(27).其中由于溶剂水诱导下的化学键断裂与生成所引起了配合物(2)～(8)及(25)～(27)与配合物配体(1)间的单晶转化。3)在水热条件下,以2,3-吡嗪二甲酸单酰胺作为原料构筑了十五个两类异质同构体的2,3-吡嗪二甲酸(pyrazine-2,3-dicarboxylic acid, H2pzdc)稀土铜异核金属配位聚合物,通过单晶衍射、元素分析及IR等对配合物进行了表征。其中,pzdc2-配体采用μ2-η2：η1配位模式桥联两个[Cu2(pzdc)2]亚结构单元形成1D双桥链状结构,采用μ3-η2：η2：η1配位模式将三个RE原子桥联在一起拓展成拓扑(4,4)2D方格结构,采用μ3-η2：η1：η1配位模式将1D链和2D面构筑成3D砖墙式{4.62}2{42.62.82}{63)2{65.8}2拓扑网络结构。对Tm-Cu配合物的热重残余物进行了分析表明,得到的是Cu2Tm205, Cu2O及Tm203三个物种的混合物,采用谢勒公式计算得知其平均晶粒度D直径为46.6nm的纳米级微粒。研究了其中Eu-Cu、Tb-Cu、Sm-Cu及Dy-Cu的异核金属配位聚合物的荧光性质。更多还原

【Abstract】 The rigid ligands of multifunctional carboxylic acid with hetero atoms are one of the preferred choices for hetero-metal complex-preparing. Pyrazine carboxylic acid is a multifunction ligand with N/O-donors and could be employed in linking different metal atoms with different coordinative modes, resulting in unexpected structural hetero-metal polymers. In this dissertation, on one hand,5-methylpyrazine-2-carboxylic acid (Hmpca) is selected as the complex-ligand, six3d-4f, one3d-3d and one3s-3d hetero-metal coordination polymers were obtained and structurally characterized. On the process of preparation of hetero-metal complexes with copper complex-ligand, there exits crystal transformation between six types of products and complex-ligands based. On the other hand, pyrazine-2,3-dicarboxylic acid monoamide was selected as the material and assembled with rare-earth metals and copper metal resources under hydrothermal condition.15Rare earth (RE)-copper hetero-metal coordination polymers were obtained and their motifs and functional properties were also discussed.In the first part, one2D corrugated plane hetero-metal coordination polymer was constructed by Ni(II) complex-ligand and AgNO3in solution reaction. Seven1D or2D hetero-metal complexes (2)-(8) were prepared based on Cu(II)-complex-ligand and RE/main group metal ions in water. Structural analysis indicates that (2)-(3) and (5)-(8) are isostructural. The pH and the types of alkali are critical roles on the resultant products, the employment of NaOH or LiOH, CsOH and RsOH in modulating pH values did not result in any hetero-polymers products. However, a new2D Cu-K complex (4) was obtained in the presence of KOH, in which the Cl-balances the charge and serves as the template.In the second section,15RE-Cu coordination polymers with pyrazine-2,3-dicarboxylic acid are formed under hydrothermal condition. Single crystal diffraction indicates the15complexes are assigned to two types of isostructural motifs. All the compounds were characterized by elemental analysis and IR, etc. The pyrazine-2,3-dicarboxylate (pzdc2-) adopts μ2-η2:η1mode and connectes Cu(II) atom into1D double chain, while it links three RE atoms via μ2-η2:η1fashion into a2D (4,4) grid network. Finally, the structure can be described as the3D brick-like{4.62}2{42.62.82}{63}2{65.8}2topology. Shaler formula calculation shows that its average diameter crystallite size is46.6nm micro-particles. The fluorescence emission spectra of Eu-Cu、Tb-Cu、Sm-Cu and Dy-Cu complexes are also investigated.In the last, a new compound [Cu(mpca)2](25) with5-methylpyrazine-2-carboxylic acid was obtained in CH3OH.[Cu(Hmpca)2(H2O)2]·2NO3·2H2O (26) was diretcly obtained by [Cu(mpca)2(H2O)]·3H2O and La(NO3)3under mild conditions. While a new {[Cu(mpca)(μ-Cl)(H2O)]·H2O}n (27) compound was also prepared via RECI3and [Cu(mpca)2(H2O)]·3H2O in the presence of NaOH.(25)～(27) and (2)～(8) complexes exit single crystal transformation between the resulting compounds and complex-ligand matrix, in which water media induces the break of bond-bond formation and generate crystal transformation.更多还原