【作者】 原路彤；

【导师】 王作祥；

【作者基本信息】 东南大学 ， 应用化学， 2006， 硕士

【摘要】 咪唑及其衍生物与过渡金属离子配合物一直引起人们很大的关注,其中一些配合物在光、磁、催化和生物活性等方面有广阔的应用前景。本文合成和表征了2-（2-吡啶基）咪唑配合物和2-甲基咪唑配合物,并测定了它们的晶体结构。本论文工作分为如下三部分:1.以2-吡啶甲醛为原料合成了2-（2-吡啶基）咪唑化合物（PyIm）,并测定了晶体结构。晶体结构研究表明,2-（2-吡啶基）咪唑中两个独立芳环,吡啶环及咪唑环并不共平面,存在10.70°的平面夹角。2.制备了配合物[Cu（PyIm）₂Cl₂]·H₂O、[Cu（PyIm）₂（H₂O）]SO₄·3H₂O和[C₄H₇N₂]₂[Mn（C₄H₆N₂）₂（Sal）₂][Mn（CH₃OH）₂（Sal）₂]·2CH₃OH,并测定了这三个配合物的晶体结构。配合物[Cu（PyIm）₂Cl₂]·H2O的中心铜（II）离子具有畸变八面体构型（CuCl2N2N′2）。配合物[Cu（PyIm）₂（H₂O）]SO₄·3H₂O的中心铜（II）离子具有三角双锥构型（CuN2N′2O1）。配合物[C₄H₇N₂]₂[Mn（C₄H₆N₂）₂（Sal）₂][Mn（CH₃OH）₂（Sal）₂]·2CH₃OH分子由两个独立的配离子[Mn（III）（C₄H₆N₂）₂（Sal）₂]–和[Mn（III）（CH₃OH）₂（Sal）₂]–、两个质子化的2?甲基咪唑正离子[C₄H₇N₂]+和两个溶剂甲醇分子构成。配离子[Mn（III）（C₄H₆N₂）-2（Sal）₂]–和[Mn（III）（CH₃OH）₂（Sal）₂]–的中心锰（III）离子都具有中心对称的畸变八面体构型。3.测定了铜（II）配合物[Cu（PyIm）₂Cl₂]·H₂O和[Cu（PyIm）₂（H₂O）]SO₄·3H₂O的低温ESR, [Cu（PyIm）₂Cl₂]·H₂O的g‖=2.2951（A‖=145G）,g⊥=2.0901;配合物[Cu（PyIm）₂（H₂O）]SO₄·3H₂O的g=2.1187。测定了配合物[Cu（PyIm）₂Cl₂]·H-2O、[Cu（PyIm）₂（H₂O）]SO₄·3H₂O及[C₄H7N₂]₂[Mn（C₄H₆N₂）₂（Sal）₂][Mn（CH₃OH）₂（Sal）₂]·2CH₃OH在稀溶液中的电子光谱及热重分析数据。热重分析表明,随着温度的升高,三个配合物首先失去结晶水分子或溶剂甲醇分子,随后配合物在更高温度下逐步发生热分解。测定了配合物[C₄H₇N₂]₂[Mn（C₄H₆N₂）₂（Sal）₂][Mn（CH₃OH）-2（Sal）₂]·2CH₃OH的变温磁化率（1.8-300K）。当C=6.01097,θ=-1.67364时,能很好地符合Curie-Weiss定律。在6-300K温度范围内,配合物的有效磁矩为6.10-6.91BM。更多还原

【Abstract】 The complexes of imidazole and its derivatives with transition?metal ions have gained considerable attention for a long time,and some of them can be used potentially to optics,magnetic,catalysis and bioactivities. In order to synthesize and research the complexes of transition?metal ions with imidazoles,the complexes of 2-（2-pyridyl）imidazole and 2-methyl imidazole have been synthesized and characterized,and their crystal structures were determined by X-ray analysis. The thesis is composed of the following three sections:Part I. 2-（2-pyridyl）imidazole （PyIm） was synthesized from pyridine-2-aldehyde,and its crystal structure was determined by X-ray analysis. The crystal structure of PyIm·CH₃COOC₂H₅ shows that the two aryl rings of imidazole ring and pyridine ring in 2-（2-pyridyl）imidazole do not share a common plane, the dihedral angle between them is 10.70°.Part II. The complexes of [Cu（PyIm）₂Cl₂]·H₂O、[Cu（PyIm）₂（H₂O）]SO₄·3H₂O and [C₄H₇N₂]₂[Mn（C₄H₆N₂）₂（Sal）₂][Mn（CH₃OH）₂（Sal）₂]·2CH₃OH have been prepared , and their crystal structures were determined by X-ray analysis. The copper（II） ion of [Cu（PyIm）₂Cl₂]·H₂O has a distorted tetragonal?octahedral geometry with CuCl2N2N′2,and the copper（II） ion of [Cu（PyIm）₂（H₂O）]SO₄·3H₂O has a trigonal?bipyramidal geometry with CuN2N′2O1.The complex of [C₄H₇N₂]₂[Mn（C₄H₆N₂）₂（Sal）₂][Mn（CH₃OH）₂（Sal）₂]·2CH₃OH consists of two independent anions of [Mn（III）（C₄H₆N₂）₂（Sal）₂]– and [Mn（III）（CH3OH）₂（Sal）₂]–,combined together with two cations of protonated 2-methylimidazole molecules and two methanol molecules of solvation. Both the manganese（III） ions of [Mn（III）（C₄H₆N₂）₂（Sal）₂]– and [Mn（III）（CH₃OH）₂（Sal）₂]– have centrosymmetric and distorted tetragonal?octahedral geometries.Part III. The ESR spectra of [Cu（PyIm）₂Cl₂]·H₂O and [Cu（PyIm）₂（H₂O）]SO₄·3H₂O were measured at low temperature （110K）. The g?values of [Cu（PyIm）₂Cl₂]·H₂O are g‖=2.2951 with A‖=145G and g⊥=2.0901,and that of [Cu（PyIm）₂（H₂O）]SO₄·3H₂O is g=2.1187. The electronic absorption spectra in thin solution and thermal gravimetric analyses of [Cu（PyIm）2Cl2]·H2O、[Cu（PyIm）₂（H₂O）]SO₄·3H₂O and [C₄H₇N₂]₂[Mn（C₄H₆N₂）₂（Sal）₂][Mn（CH₃OH）₂（Sal）₂]·2CH₃OH were also measured. Thermal gravimetric analyses shows that as temperature rises, the three complexes loses first their crystal water or methanol molecules of salvation,and then decompose更多还原