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However, the thermal stability of metallic coordination polymer hardly enhanced in comparison with the polymer never coordinated transitional metallic ions. The reason might be that the energy of coordinate bond formed between metallic ion and polymer was trival in comparison with that of covalent bond in polymer. It started with coordinate bond when the coordinate polymer decomposed under high temperature, so it engendered little for the thermal stability at high temperature.

而金属配聚物较未配位金属的配体高温热稳定性提高不大,可能是由于金属离子与配体之间形成配位键的键能与配位体内的共价键键能相比要小得多,当金属配聚物受热裂解时,首先从配位键开始,因此对高温热稳定性的影响甚微。

Result showed that tetrasubstituted calix [4] arenes in lower rim were stronger complex abilities than bisubstituted calix [4] arene with transition metal, heavy metal and rare earth ions. But when introducing the aminephenolicalcohols in the 1, 3-bisubstituted calix [4] arenes, the complex abilities were improved.

结果表明:在Lower rim上四取代的杯[4]芳烃配体比1,3-二取代的杯[4]芳烃配体对过渡金属离子,重金属离子及稀土离子有更好的配位能力,但当1,3-二取代的取代基上引入醇胺链型配体时,对金属离子也有很好的配位能力。

The results showed that the mole ratio of three ligands to CoCl_2, NiCl_2 were 1:1 and to CuCl_2, ZnCl_2, CdCl_2 were 2:1, The IR, UV-Vis and FS of complexes were investigated. Their IR peaks were classified as the corresponding groups or bonds; The relation of their structure with the conjugative effects, absorbtion wavelength and molar absorb coefficients were discussed with the UV-Vis and FS.

结果表明:噻唑类配体与金属CuCl_2,CdCl_2配位比分别2∶3和3∶2,至于配位机理还需进一步探讨;硒二唑配体与CoCl_2和NiCl_2配位比均是1∶1,而与CuCl_2、ZnCl_2和CdCl_2的配位均为比2∶1;对配合物的IR吸收峰进行了归类与指认,并对配合物的紫外和荧光光谱进行讨论分析,推测硒二唑类化合物与金属发生配位的部位是v中Se原子与金属配位。

From the structural analysis of three praseodymium complexes, we could draw a conclusion that as the dentate arms of carboxyl group on ligands elongating, the coordination numbers of Pr and the coordination modes of ligands increase, and the mean distances between metallic atoms of metallic helices existing in these complexes augment.2. By altering 5-substituting group of isophthalic acid three series of lanthanide complexes 8~19 with 5-methylisophthalic acid and 5-nitroisophthalic acid have been prepared.

从得到的三个配体的镨配合物的结构分析可以看出,随配体的羧基齿臂的增长,Pr的配位数逐渐增大,配体的配位模式增多,配合物中存在的螺旋金属链中的金属间平均距离增大。2、通过改变间苯二甲酸配体的5位取代基,制备了5-甲基间苯二甲酸和5-硝基间苯二甲酸的三个系列稀土羧酸配合物8~19。

Furthermore, the one-dimensional complexes 26 and 28 with strongπ-πpacking interactions are prepared from DMF solvent, which indicates that the traditional solvent volatilizing method could bring low-dimensional complex.4. By measuring the enthalpy changes of the liquid phase formation reaction for complexes a~e, and calculating the electronic densities of five 5-substituted derivation of isophthalic acid, we can make a conclusion that 5-substituted group changing of the ligand has a little influence on oxygen atoms of carboxyl groups.5. Fluorescence experiments of these complexes indicated that they could be used for luminescence materials in future.6. Using packing saturation rule we calculated and analyzed these series of complexes, and the results showed that the changes of complexes with changes of ligands could be explained from the rule.

在DMF溶剂中得到了具有强π-π堆积作用力的一维配位聚合物[Ln(5-NO_2-bdc)(NO_3)]Ln=Pr(26和Ho(28),表明传统的溶剂挥发合成条件可以得到低维的配合物。4、通过配合物a~e的液相生成反应焓的测定,以及配体阳离子的电子密度计算,进一步佐证了间苯二甲酸的5位取代基变化对配体的羧基氧原子配位能力影响不大的结论。5、荧光特性表明此类配合物可以用于发光材料。6、利用堆积饱和规律对所得系列的配合物的进行计算和分析,发现随着配体的变化,配合物的变化可以从堆积饱和规律出发进行解释。

The first part is to synthesize 5-formyl -8- quinolinol from 8-uinolinol and chloroform , using ethanol as a solvent. Then analysizing the 5-formyl-8-quinolinol by IR. The second part is , according to ideas of molecule designing, to synthesize the new self-assembly Inorganic-Organic coordination polymers Co(u2-bpyV2O6,(C4H4N2)Ni2(H2O)2-V4Ol2,(Cl2Hl2N2)Co-V2O6 using Cu, Ni, and Co as templating, 4-cyano-pyridine(4-CNPy), 4,4-bipyridine,pyrazine, l,2-bis(4-pyridyl)ethane, 5-formyl -8- quinolinol as building blocks and Ammonium Metavanadate (NH4VO3) as subordinate building blocks by Hydrothermal , analysizing their content of element determining their structures by X-Ray diffraction.

本课题实验分为两部分:一是配体的合成,以8-羟基喹啉、三氯甲烷为原料,以乙醇为溶剂,合成了5—甲醛基—8羟基喹啉并且对其进行了IR的分析测定;二是配位聚合物的合成,通过分子设计,采用溶剂热法以Cu、Ni、Co为中心离子,以5—甲醛基—8羟基喹啉、4,4-联吡啶、吡嗪、1,2-二吡啶基乙烷为配体,以偏钒酸根(VO_3~-)为辅助配体,通过水热法自组装合成了新的3-D网状结构配位聚合物Co(μ_2-bpy)V_2O_6,(C_4H_4N_2)Ni_2(H_2O)_2·V_4O_(12),C_(12H_(12)N_2Co·V_2O_6,并对其进行了元素分析和晶体结构的测定。

In the thesis, a series of novel single and multi-armed oxadiazole bridging ligands and pyridyl-4, 5-imidazole dicarboxylic acid ligands have been synthesized. The coordination chemistry of these novel ligands with transition metal ions was investigated. In addition, two 1, 3, 4-oxadiazole bridging ligands end-capped by chelating Schiff-base coordination sites have been designed and synthesized. The coordination chemistry based on one of the two ligands with metal ions was primarily investigated.

本文报道了一系列新颖的含1, 3, 4-Oxadiazole杂环的单臂及多臂有机配体,研究了它们与过渡金属离子的配位反应化学;合成了吡啶基-4,5-咪唑二羧酸有机配体,研究了它们在水热条件下与过渡金属离子的配位反应化学;另外,还合成了1, 3, 4-Oxadiazloe杂环桥联的双Schiff-base有机配体,初步探讨了其与过渡金属离子的配位反应化学。

L acted as tridentate ligand to chelate with metal atom in enol and ketone form respectively; In complex anion Co atom reside in tetrahedral coordination environment.

钴原子位于八面体配位环境中,配体L分别以烯醇式和酮式充当三齿配体与金属原子配位,配阴离子中Co原子位于四面体配位环境中。

Complexes 7-12, 16, 22 and 23 are dimeric molybdatesor dimeric tungstates, the central metal with citrate or malate in a molar ratio of 1:1. Theanions of these complexes have two metal atoms and two ligands. Each ligand acts as atridentate fashion via theirα-alkoxy,α-carboxy andβ-carboxy groups coordinated to eachmetal atom. Complex 13 is a monomeric molybdate. The citrate ligand coordinates tomolybdenum with itsα-alkoxy,α-carboxy andβ-carboxy groups in a tridentate mode.

其配阴离子中都含有2个金属原子和2个配体,且配体均以α-烷氧基、α-羧基和β-羧基氧与中心金属三齿配位。13是单核柠檬酸钼配合物,柠檬酸也以α-烷氧基、α-羧基和β-羧基氧与钼三齿配位。17和21分别为苹果酸钼、柠檬酸钨单核配合物,其中苹果酸、柠檬酸配体均以α-烷氧基氧和α-羧基氧与金属双齿配位。

The central 5, 5'-disubstituted bipyridine units of each ligand coordinate theNi or Fe ion, while all the terminal 6-monosubstituted bipyridine units of the ligands keep free of coordination, as the result trinuclear triple-stranded helicate 〓 can not form. This is considered to be caused by the steric hindrance of the methylene substituents α to the chelating nitrogens of the terminal bipyridine units and the strain caused by linkage mode.

配体L〓与Ag作用得到〓,两个配体链相互缠绕着两个Ag离子周围形成双股螺旋结构并以头尾式排列(见图3),由于配体中位于配位N原子α或β位的末端甲基或次甲基取代基的空间位阻阻碍了头对头式异构体的形成,也正是由于配体头尾式排列而使Ag双股螺旋得以形成,这一结果表明该螺旋体的组装过程中自发地采取了空间阻碍尽可能小的那个构型。

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