【作者】 杨莉宁；

【导师】 张逢星；

【作者基本信息】 西北大学 ， 无机化学， 2006， 硕士

【摘要】 过渡金属与咪唑配体所形成的配合物以其多样的结构和广泛的用途愈来愈受到人们的重视。该类配合物在催化、生物活性及功能材料等领域都有广泛的应用前景。论文以2,2’-联眯唑及其衍生物的配合物在超分子化学中的应用和发展为研究背景,查阅大量文献后综述和评价了2,2’-联咪唑及其衍生物的配合物的研究进展,设计合成了过渡金属的2,2’-联咪唑及其衍生物配合物。 主要完成的工作如下: 1.合成了2,2’-联咪唑（H₂biim）。以此为配体,与过渡金属离子Zn²⁺、Mn²⁺、Cd²⁺、Co²⁺、Ni²⁺、Cu²⁺等的二酸盐或卤化物进行水热条件反应或一般条件的反应,制备合成了8种配合物晶体。通过红外光谱、紫外一可见光谱对其进行了成键分析。单晶结构分析表明:联咪唑为一刚性配体,容易进行二齿鳌合配位,常得到单核配合物;未配位的两个含氢氮原子是一对良好的给电子体,极易与电子受体羧基氧原子形成R₂²（9）氢键而连接成一条链,同时也易与卤原子或碳原子之间形成氢键,加之咪唑环之间也容易产生π-π堆积相互作用,最终会形成二维网状结构或三维立体结构的超分子。热分析测试表明,通过水热合成的配合物比一般合成的热稳定性好。 2.在2,2’-联咪唑的基础上,合成了2,2’-联咪哗的二甲基衍生物——N,N’-二甲基-2,2’-联咪唑（Me₂biim）配体,与过渡金属离子Zn²⁺、Ag⁺、Cu²⁺、Co²⁺、Ni²⁺等的无机盐反应,制备了6种配合物,其中首次以水热合成法得到了一种一维螺旋链聚合物[Zn（μ-Me₂biim）Cl₂]_n（9）的单晶。单晶结构分析表明:Me₂biim由于甲基的位阻效应,容易以桥联方式与金属进行单齿配位,从而形成多核配合物或螺旋链聚合物。荧光光谱证明配体Me₂biim有一定的荧光性,当与金属锌形成配合物时,其荧光强度增大。热分析表明该聚合物热稳定性好,且配体是逐步从配合物中分解的。通过摩尔电导、红外光谱、紫外—可见光谱对其它配合物进行了成键表征。更多还原

【Abstract】 The transition metal coordination compounds with imidazole and its derivatives are more and more important as their various structures and extensive uses in the field of catalysis, bioactivity, and material etc. Therefore, 2,2’-biimidazole, its methyl derivatives ligands and their transition metal complexes in the paper have been synthesized and characterized.The main work is as follows:1. The 2,2’-biimidazole （H₂biim） ligand and eight corresponding complexes with transition metal ion Zn²⁺, Mn²⁺, Cd²⁺, Co²⁺, Ni²⁺and Cu²⁺ have been designed and synthesized, in which eight single crystals were abotaind. These complexes are characterized by IR spectrum, UV-Vis spectrum, thermal analysis and structural analysis. The structural analysis of complexes show that H₂bbiim usually behaves as a chelating bidentate ligand for it’s a rigidity group, and mononuclear compounds were often obtained. Furthermore, H₂biim can act as a donor in hydrogen bonding interactions, in this case, two oxygen atoms of a carboxylate group can join directly to the N-H donors via a charge-assisted heteromeric hydrogen-bonded synthon of R₂²（9）, extending into multidimensional networks in definite directions. In addition to, there also exist hydrogen bonding interactions between the N-H donors of H₂biim and haloid atoms or carbon atoms. Moreover, there are strong π-π stacking interaction in adjacent imidazoles, which resulted in two-dimensional network structure so much as three-dimensional stereo structure. The TG studies of the complexes synthesized under hydrothermal condition are more stable than those under common condition.2. The N,N’-dimethyl-2,2’-biimidazole ligand（Me₂biim） and six corresponding complexes with transition metal ion Ag⁺, Co²⁺, Ni²⁺, Cu²⁺ and Zn²⁺ have been designed and synthesized on a basis of H₂biim. These complexes are characterized byIR spectrum, UV-Vis spectrum and molar conductance. A new helix coordination polymer [Zn（u-Me2biim）Cl2]n has been obtained under hydrothermal condition and was characterized by thermal analysis, photoluminescence spectrum and single crystal structural analysis additionally. The results indicate that the Me2biim ligand form dinuclear and polymeric structures with unidentate coordination, since the methyl steric requirements force the two imidazole rings out of coplanarity. Free Me2biim exhibits a weak emission of fluorescence. A comparison of the fluorescence spectra of the Me2biim ligand and its Zn complex demonstrate that the emission of fluorescence was strongly enhanced in the Zn compound. Thermal analysis indicates that the Zn complex is stable until to 355 "C, and then the ligand start to decompose step by step.3. The N-methyl-2,2’-biimidazole ligand （MeHbiim） and two corresponding complexes with transition metal ion Cd2+ and Mn2+ have been synthesized. These complexes are characterized by IR spectrum, UV-Vis spectrum and Molar conductance. Thereinto, a novel coordination polymer [Cd3（MeHbiim）2（u-tere）3]n has been obtained under hydrothermal condition in the first time and was characterized by thermal analysis, photoluminescence spectrum and structural analysis additionally. The structural analysis indicates that the MeHbiim behaves as a chelating bidentate ligand similar to the H2biim ligand except the weak rigidity. And hydrogen bonding interactions between the N-H donor of MeHbiim and the charge acceptor atoms is still existed. Due to the variety of the coordinated mode of the terephthalate, a linear trinuclear Cd polymer with 3-D topology was formed. Photoluminescence spectrum showed highly enhanced fluorescence intensity in Cd polymer comparing to free MeHbiim ligand.更多还原