【作者】 祝婕；

【导师】 尹显洪； 林翠梧；

【作者基本信息】 广西大学 ， 有机化学， 2008， 硕士

【摘要】 吡唑、三氮唑及其衍生物的金属配合物由于它的广谱生物活性、特殊的电磁性能、配位性能及光化学性能等在多种领域中的潜在应用引起人们极大兴趣。为了研究和讨论吡唑、三氮唑类配体及其配合物的结构与性质关系,本文共用水热法合成12个未被报道的新晶体。其中合成配体晶体2个,金属配合物晶体10个,并测定解析了它们的晶体结构,并对其进行了谱学表征,部分配合物做了抑菌活性测试。利用3-甲基-5-吡唑甲酸（pyra）为原料分别合成了配合物{[Cu（pyra）₂（H₂O）]·3H₂O}_n（1）、{[Cu₂（pyra）₂（2,2’-bipy）（4,4’-bipy）₂]·6H₂O}_n（2）。配合物（1）Cu（Ⅱ）离子的配位环境为五配位金字塔构型,配合物（2）Cu（Ⅱ）离子的配位环境为五配位金字塔构型。以1,2,4-三氮唑-3-甲酸（Tria）为配体,合成了三个结构类似的单核配合物[Cu（tria）₂（H₂O）₂]_n（3）、[Zn（tria）₂（H₂O）₂]_n（4）、[Cd（tria）₂（H₂O）₂]_n（5）。Cu（Ⅱ）、Zn（Ⅱ）、Cd（Ⅱ）的配位环境均为六配位的扭曲八面体构型。引入第二配体1,10-phen,合成了两个结构类似的配合物{[Cu（tria）（phen）Cl]₂}_n（6）、[Cu（tria）（phen）NO₃]_n（7）,Cu（Ⅱ）配位环境均为五配位的扭曲金字塔构型。对于以上五种配合物做了抑菌活性测试,通过对比最低抑制浓度（MIC）得出,配合物（6）的抑菌活性最好,配合物（3）、（5）的抑菌活性最差。以Pb盐、Tria为原料,合成了两个结构类似的配位聚合物（8）、（9）,Tria作为四齿桥联配体。配合物（8）中,氯离子以μ₂-Cl的形式参与配位连接两个铅离子,Pb配位数为八。配合物（9）中,SCN^-阴离子以μ₂-N的形式参与配位连接两个铅离子,Pb配位数为七。以1,2,4-三氮唑-3-甲酸甲酯为原料,合成并培养出了Triam晶体。又以Cu离子、Triam和phen为原料,合成了一维Z字链状配位聚合物（10）,Triam作为三齿桥联配体。配合物分子之间以氢键组装成三维空间结构,形成许多大的隧道孔穴,孔穴中存在结晶水分子和硝酸根离子。以1,2,4-三氮唑-3-甲酸甲酯为原料,合成并培养出了一个酰腙晶体Triaah,晶胞中每个结构单元包含四个独立的酰腙分子和一个结晶水结构单元。氢键和π-π堆积作用将配合物分子连接成空间三维结构。更多还原

【Abstract】 A considerable interest has been focused on a series of derivatives and metal complexes of pyrazole and triazole because of their broad bio-activities, special electromagnetic and coordination properties being used in their potential application.In order to investigate the relationship between the structure and property of pyrazole,triazole and their complexes,twelve complexes had been synthesized by hydratethermal synthesis,including two ligand crystals and ten complex crystals.Their crystal structures,spectrum characters had been characterized,some with antibacterial activities.The complexes {[Cu（pyra）₂（H₂O）]·3H₂O}_n（1）and {[Cu₂（pyra）₂（2,2’-bipy） （4,4’-bipy）₂]·6H₂O}_n（2）have been obtained by taking pyra as a starting material. In the complexe（1）,Cu（Ⅱ）adopts five-coordinated distorted pyramid geometry. In the complexe（2）Cu（Ⅱ）adopts five-coordinated distorted pyramid.Three similar mononuclear complexes[Cu（tria）₂（H₂O）₂]_n（3）,[Zn（tria）₂ （H₂O）2]_n（4）and[Cd（tria）₂（H₂O）₂]_n（5）have been synthesized by the reaction between Tria and metal salts,with Cu（Ⅱ）,Zn（Ⅱ）and Cd（Ⅱ）adopt six-coordinated distorted octahedron geometry.After adding to the second ligand,we obtained two similar complexes {[Cu（tria）（phen）Cl]₂}_n（6）and [Cu（tria）（phen）NO₃]_n（7）with Zn（Ⅱ）in the center of the distorted pyramid geometry.We did the test of antibacterial activity of the five complexes and made the conclusion by compared to MIC.The test result indicate that the complex（6）show good activity and complex（3）and（5）shows no activity.Two three-dimensional Pb polymers（8）and（9）have been prepared by using Pb salt and Tria,with Tria considered as quadridentate ligand.In the complex（8）, Cl acted as aμ₂-Cl bridging ligand links two Pb ions and Pb is eight coordinated.In the complex（9）,SCN^- acted as aμ₂-N briding ligand links two Pb ions and Pb is seven coordinated.We cultivate a ligand crystal Triam by using methyl 1,2,4-triazole-3-carboxylate as the starting material.Then the one-dimensional Z configuration chain polymer（10）is obtained by using Cu salt,Triam and phen with Triam as the trident-bridging ligand.Complexes was assembled with H-bonds to three-dimensional network so as to form a lot of tunnel cavities which filled with hydrates and nitrates.We cultivate a ligand crystal Triaah by using the starting substance methyl 1,2,4-triazole-3-carboxylate.Every cell contain a unit of four independent hydrazones molecules and a hydrate.Complexes are linked with H-bonds andπ-πinteractions to form a three-mensional network.更多还原