摘要
配位化合物具有新颖的拓扑结构及在功能材料和分子识别等方面的潜在应用前景，已成为近年来人们关注的焦点。1,2,4-三氮唑和吡嗪类衍生物具有配位能力强，配位点多，配位方式多样等优点，可以以多种方式桥联金属离子和其它配体，广泛的用于功能配合物的构筑。
本文合成了两种3,5-二取代-1,2,4-三氮唑化合物、一种吡嗪酰胺配体和一种3,5-二取代-1,2,4-三氮唑过渡金属配合物，并采用熔点测定、红外光谱、核磁共振氢谱和X-射线单晶衍射等方法进行了表征，对配合物的热稳定性和变温磁化率进行了初步的研究。
主要工作如下：
1.合成了以3,5-二(羟甲基)-1,2,4-三氮唑为配体的三维的双核钴（Ⅲ）配合物，并对配合物的晶体结构进行了分析，发现3,5-二(羟甲基)-1,2,4-三氮唑配体中特有的氢键模式是中心金属离子配位方式的一个重要因素。并对其热性能和变温磁化率进行了研究，预测了该配合物的磁性。
2.以乙醇酸与水合肼为原料,经缩合成环、氯化、巯基化三步反应,合成了尚未见文献报道过的4-氨基-3,5-二(巯基甲基)-1,2,4-三氮唑柔性配体化合物,并用采用熔点测定仪、元素分析、红外光谱、核磁共振氢谱等方法进行了表征,并讨论了其合成条件、光谱特性和功能性应用。
3.以乙酸和水合肼为原料，经缩合成环、氧化后得到三氮唑羧酸，三氮唑羧酸进一步酯化后再与水合肼发生酰肼化反应,得到二取代的酰肼三氮唑与吡啶甲醛反应，通过传统方法设计合成了一种含吡啶环的3,5-二取代-1,2,4-三氮唑希夫碱配体。并用采用熔点测定仪、元素分析、红外光谱、核磁共振氢谱等进行表征,并讨论了其合成条件、光谱特性等性质。
4.以吡嗪-2,3-二甲酸为原料，经过酯化、酰胺化两步反应设计合成了一种吡嗪酰胺化合物，对该化合物进行了熔点、元素分析、红外光谱(IR)、氢核磁共振光谱(1H-NMR)等结构表征，并对该配体的配位进行了探讨。
In recent years, coordination compounds with novel structure topological havepotential applications in functional materials and molecular recognition,have causedgreat attention. 1,2,4-triazole and pyrazine derivatives with many advantages:strongcoordination ability, more coordination points and more patterns, can be bridging invarious ways with metal ions and other bridging ligand, widely used in theconstruction of the functional complexes.
In this study，two 3,5 - disubstituted-1,2,4 - triazoles and one pyrazine-amideligands have been synthesized, a kind of 3,5- disubstituted -1H-1,2,4 - triazolescomplex with transition metales has also been synthesized and characterization bymelting point,IR, 1H-NMR and X-ray crystal diffraction, thermal stability andmagnetic susceptibility of the complex have been conducted.
Our main works are as follows:
1. 3,5- bis (hydroxymethyl) -1,2,4– triazole was chosen as ligand.Its binuclearcobalt Co(Ⅲ)complex was synthesized and the crystal structure of the complexeswere analyzed .We found that specific hydrogen bonding pattern of 3,5 - bis(hydroxymethyl) -1,2,4 - triazole ligands is an important factor for the bonding modeof center metal ions.The thermal properties of the complex have been studied.Itsmagnetic susceptibility has also been predicted.
2. 4-amino-3, 5 - bis (mercapto methyl) -1, 2,4 - triazole flexible ligandsynthesized with glycolic acid and hydrazine hydrate by three reaction steps:condensation, chlorination and thiol reaction. As a new flexible triazole ligand，hasnot been synthesized and reported before.It has been characterization by melting point,elemental analysis,infrared spectroscopy and 1H-NMR spectroscopy.Synthesisconditions, spectroscopic properties and functional applications were characterizedand discussed.
3. 3,5 - disubstituted -1,2,4 - triazole Schiff base ligand containing pyridine ringsynthesized with acetic acid and hydrazine hydrate by condensation, and thenoxidation to triazole carboxylic acid, triazole carboxylic acid reacted with hydrazinehydrate and then further esterification reaction occurs to hydrazine. By reaction ofdisubstituted triazole hydrazine with 2 - pyridine - formaldehyde, synthesized by traditional methods. Characterized by melting point, elemental analysis, infraredspectroscopy, 1H-NMR spectroscopy. Its synthesis conditions, spectroscopicproperties and other properties have been discussed.
4. Pyrazinamide synthesized by two-step reaction with pyrazine 2,3 - dicarboxylicacid as raw material, through esterification, amidation, the compounds wascharacterized by the melting point, elemental analysis , infrared spectroscopy (IR),proton nuclear magnetic resonance spectroscopy (1H-NMR)，its composition andcoordination mode have been discussed.
引文
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