【作者】 郭桂全；

【导师】 梁宏； 边贺东；

【作者基本信息】 广西师范大学 ， 无机化学， 2005， 硕士

【摘要】 酰肼类化合物具有很强的配位能力,能与许多金属形成配合物, 在磁性材料、光学材料、分子识别、催化、生物活性等方面具有很大的应用价值。而硫代半卡巴腙类化合物也是较强的配位剂,形成的配合物对于抗结核、麻风、风湿、疟疾、病毒、天花和某些肿瘤有一定的药物活性。锌、镍、钴是生物体内的必需元素,它们在生命体中大多以配合物形式存在。所以本文设计合成了一个双酰肼配体和两个相应的Zn（II）、Co（II）配合物,以及一个硫代半卡巴腙配体和两个相应的Zn（II）、Ni（II）配合物,并用IR、UV-Vis、TG-DTA、荧光、固态荧光、元素分析等实验手段对所合成的配合物进行了性质表征,并研究了它们与CT-DNA作用的键合模式,实验数据表明它们都是潜在的DNA探针,有一定的研究价值。其中吡啶-3-甲醛缩氨基硫脲Zn（II）配合物还具有抑菌活性,是潜在的治疗药物。本论文分为以下两部分: 第一章:合成了一种新颖的不对称双酰肼类配体苯甲酰异烟酰肼C13H11N3O2,并通过溶液法合成了它的Zn（II）、Co（II）配合物,X-射线单晶衍射实验表明:两配合物的经验式分别为[Zn(C₁₃H₁₁N₃O₂)₂Cl₂] ·2H₂O 1 、[Co(C₁₃H₁₁N₃O₂)₂Cl₂（H₂O）₂]·2H₂O 2. 其中配合物1 为正交晶系,空间群为Pmn21,a = 28.58（2）A|°, b = 6.118（5）A|°, c = 7.762（6）A|°, Z = 2, R₁ = 0.0670, wR₂ = 0.1504,配位构型为四配位的四面体;而配合物2 为单斜晶系,空间群为P2₁/n,a = 22.06（4）A|°, b = 6.251（11）A|°,c = 22.73（4）A|°,Z = 4, R₁ = 0.0774, wR₂ = 0.1406, 配位构型为六配位的八面体。测定了它们的红外光谱,以及与CT-DNA 相互作用的紫外-可见光谱、荧光光谱,另外还测定了1 的固态荧光、差热-热重等性质。光谱研究表明,1 和2 都能以插入方式与CT-DNA 键合。第二章:根据已报道的文献,合成了硫代半卡巴腙类配体吡啶-3-甲醛缩氨基硫脲,并通过溶剂热法、溶液法分别合成了它的Ni（II）、Zn（II）配合物,经验式分别为[Ni（C₇H₇N₄S）₂] 3、[Zn（C₇H₇N₄S）₂（H₂O）₂（CH₃CH₂OH）₂]（NO₃）₂ 4. 其中配合物3为单斜晶系,空间群为P2₁/c,a =5.4774（16）A|°,b = 19.865（6）A|°,c = 7.530（2） A|°,Z = 2,R₁ = 0.0303,wR₂ = 0.0656,配位构型为四配位的平面四边形构型;而配合物4为三斜晶系,空间群为Pī,a = 8.054（3）A|°,b = 8.936（3）A|°,c = 11.208（4）A|°,Z = 1,R₁ = 0.0254,wR₂ = 0.0707,配位构型为六配位的八面体构型。测定了它更多还原

【Abstract】 Hydrazidate and its ramification are strong chelating ligands, which can form complexes with many metals. These compounds have prodigious application values, such as magnetism and optical material, molecule recognize reagent, catalyse reagent, especially in biological activity aspect. And thiosemicarbazone also possess strong coordination ability, its complexes have druggery activity, such as antitumor, restraining lepra, rheumatism, impaludism, virus, smallpox. Zinc, Nickel and Cobalt are necessary elements, which is reported that they exist in the form of complex. Therefore, in this essay, we synthesized one dihydrazidate ligand and its two complexes, and one thiosemicarbazone ligand and its two complexes. The complexes were characterized by UV-Vis, fluorescence, solid fluorescence, TG-DTA, element analysis and IR spectrum and the crystal structures are determined by single crystal X-ray diffraction methods. And their bond model with CT-DNA has also been investigated, data indicates that they all are potential DNA probe and have investigated values. Thereinto, pyridine-3-carboxaldehyde thiosemicarbazone Zn（II） complex has antiviral activity, which is potential therapy druggery. Chapter one: A new unsymmetrical dihydrazidate ligand C₁₃H₁₁N₃O₂ is synthesized, and its Co（II）、Zn（II） complex are synthesized by liquid method, which formula are [Zn(C₁₃H₁₁N₃O₂)₂Cl₂]·2H₂O 1、[Co(C₁₃H₁₁N₃O₂)₂Cl₂（H₂O）₂]·2H₂O 2. Complex 1 belongs to orthorhombic system, space group Pmn21,with unit cell parameters: a = 28.58（2）A|°, b = 6.118（5）A|°, c = 7.762（6）A|°, Z = 2, final R₁ = 0.0670, wR₂ = 0.1504（I>2 σ（I））, while complex 2 belongs to monoclinic system, space group P21/n,a = 22.06（4） ?, b = 6.251（11） ?,c = 22.73（4） ?,Z = 4, final R1 = 0.0774, wR2 = 0.1406（I>2 σ（I））. And complex 1 is four-coordinated tetrahedron geometry; while complex 2 is six-coordinated distorted octahedral geometry. Spectrum data indicate that the two complexes all can intervene into DNA two-strands . Chapter two: According to literature, pyridine-3-carboxaldehyde thiosemicarbazone Ni（II）、Zn（II） complexes have been synthesized. Their formulas are [Ni（C7H7N4S）2] 3、[Zn（C7H7N4S）2（H2O）2（CH3CH2OH）2]（NO3）2 4. Complex 3 belongs to monoclinic system, space group P21/c,a = 5.4774（16） ?,b = 19.865（6） ?,c = 7.530（2） ?,Z = 2,R1 = 0.0303,wR2 = 0.0656（I>2 σ（I））, while complex 4 belongs to triclinic system, space group Pī,a = 8.054（3）?,b = 8.936（3） ?,c = 11.208（4） ?,Z = 1,R1 = 0.0254,wR2 = 0.0707（I>2 σ（I））. Complex 3 is four-coordinated planer quadrangle geometry, while complex 4 is six-coordinated distorted octahedral geometry. Spectrum data indicate that the two complexes all can intervene into DNA two-strands. In the same time, we have investigated the two complexes’bacterium-restraining activities, indicating complex 4 have good restraining function to coccus, while complex 4 is not so likely due to its hardy-soluble.更多还原