【作者】 徐锁平；

【导师】 刘炯天； 冯莉；

【作者基本信息】 中国矿业大学 ， 化学工艺， 2013， 博士

【摘要】 过渡金属螯合物的形成特征是过渡金属中心原子（或离子）具有空的d轨道，能接受孤对电子，与某种能提供孤对电子的双齿配体中的配位原子以配位键相结合可形成螯合物。过渡金属螯合物的显著特性是具有较高的热力学稳定性，其稳定性由过渡金属离子、有机螯合剂、螯合环三个方面的因素决定。基于过渡金属螯合物的稳定性和其结构的特殊性质，近年来在催化剂、功能材料、生物活性等领域有着广泛的应用，是当前配位化学的研究热点之一。Schiff碱是一类含有O、N配位原子的双齿配体，与过渡金属离子有很强的配位作用，形成结构独特的过渡金属螯合物，这类螯合物在氧化还原性、催化活性、生物活性等方面表现出优越的性能，使得这类螯合物的研究成为配位化学领域的一个热点。芳香基β-二酮类配体是含有O配位原子的双齿配体，其烯醇式结构中的两个O原子与过渡金属离子有极强的配位作用，可形成稳定的螯合物，这类螯合物在磁性、荧光性能、螯合萃取、离子交换、气体储存、分子载体、生物活性等方面具有广阔的应用前景。基于Schiff碱及β-二酮类配体与过渡金属离子形成的螯合物在磁性、荧光性能、催化活性、生物活性等方面的重要应用，我们开展了卤代水杨醛Schiff碱及芳香基β-二酮过渡金属(Cu, Co, Ni, Zn, Mn)螯合物的微波固相合成、结构表征及其性质研究，具体从以下四个方面进行了研究。首先，建立了一种3,5-二碘水杨醛和5-氯水杨醛的新合成方法。该方法以水杨醛为初始原料，用碘酸盐和碘化物为碘代剂，以乙醇为溶剂，在冰醋酸和磷酸混合酸介质中，于50℃～70℃的反应温度反应2h，可得到黄色的3,5-二碘水杨醛，产率可达80%以上。以水杨醛为初始原料，以乙醇为溶剂，加入等体积的冰醋酸和浓盐酸，滴加氯酸钾水溶液，在常温下搅拌1h，得到淡黄色5-氯水杨醛固体，产率可达44%。在此基础上，设计合成了13种卤代水杨醛Schiff碱配体。其次，改进了2,4-二羟基苯乙酮的合成方法。采用微波辐射合成法，将间苯二酚、无水氯化锌与冰醋酸混合，在微波功率为150W的条件下辐射数分钟即可得到产品，产率可达68%。建立了一种2,4-二羟基-3,5-二氯苯乙酮的新合成方法，以2,4-二羟基苯乙酮为原料，加入2:1体积比的冰醋酸和浓盐酸，滴加氯酸钾水溶液，在50℃～60℃温度下搅拌1h，得到土黄色2,4-二羟基-3,5-二氯苯乙酮固体，产率可达76%。在此基础上，采用微波法合成了4种芳香基β-二酮新型配体，并通过红外光谱、元素分析、单晶X-射线衍射等方法对其进行了结构表征。第三，采用微波辐射辅助固相合成法，分别将卤代水杨醛Schiff碱配体、芳香基β-二酮配体与铜、钴、镍、锌、锰5种过渡金属盐作用，合成了65种卤代水杨醛Schiff碱过渡金属螯合物和20种芳香基β-二酮过渡金属螯合物，并培养出了32种螯合物的单晶。探索了过渡金属螯合物微波固相合成的条件，并通过红外光谱、元素分析、单晶X-射线衍射等方法对合成的螯合物进行了结构表征。最后，采用MTT（3-(4,5-二甲基噻唑-2)-2,5-二苯基四氮唑溴盐（噻唑篮））法测试了所合成螯合物对3种革兰氏阳性细菌和3种革兰氏阴性细菌的抑菌活性，探索了过渡金属螯合物与抑菌活性之间的构效关系。研究表明，中心离子的类型、螯合物的配位环境以及分子内氢键对革兰氏细菌抑制作用有不同的影响。以铜为中心离子的螯合物抑制作用为最好，镍、钴为中心离子螯合物的抑制作用居中，锌、锰为中心离子螯合物的抑制作用较弱。四配位的螯合物对革兰氏细菌的抑制能力强于六配位的螯合物。四边形结构配位环境螯合物的抑菌活性优于四面体结构配位环境的螯合物，含有分子内氢键的螯合物的抑菌活性好于不含分子内氢键的螯合物。两种卤代水杨醛Schiff碱系列的过渡金属螯合物对革兰氏细菌抑制效果明显好于芳香基β-二酮系列的过渡金属螯合物。该论文有图103幅，表78个，参考文献237篇。更多还原

【Abstract】 The transition-metal complexes are built by empty d orbitals of transition-metal ionand bidentate ligand. Transition-metal complexes have thermodynamics stability ontransition-metal ion, organic chelate reagent and chelate ring. The transition-metalcomplexes have been widely used in the field of activator, functional material,biologic activities and so on. All of the discoveries brought this field to be a focus inthe coordination chemistry.The especial structure transition-metal complexes are created by Schiff bases ofcontaining N, O bidentate ligand and transition-metal ion. The complexes exhibitsuperior performance in terms of redox, catalyse activity, biologic activity and so on.The steady transition-metal complexes are synthesized by β-diketonates with enolstructure of containing O bidentate ligand and transition-metal ion. The complex has abroad application prospect in the areas of magnetism, fluorescence, chelate extraction,ion exchange, gas storage, molecular carrier, biologic activity and so on. Importantapplications in magnetism, fluorescence, catalyse activity, biologic activity etc. basedon the complexes for Schiff bases and β-diketonates. We conduct halogen substituentsalicylaldehyde Schiff base and β-diketonates transition-metal(Cu, Co, Ni, Zn, Mn)complexes microwave solid-state synthesis, structure characterization and propertiesresearch. All research is divided into following four sections.Firstly, a new synthesis method of3,5-diiodo-salicylaldehyde and5-chloro-salicylaldehyde are presented. Salicylaldehyde, KI and KIO3were dissolvedin the mixture solution of ethanol, glacial acetic acid and phosphoric acid, followed bythe addition of water after stirring for2h at50～70℃. Plentiful yellow color prismcrystals were precipitated.Yield:>80%. Salicylaldehyde, KClO3were dissolved in themixture solution of ethanol, glacial acetic and HCl, followed by the addition of waterafter stirring for1h at the room temperature. Plentiful pale yellow color prismcrystals were precipitated. Yield:44%. On this basis,13kinds of halogen substituentsalicylaldehyde Schiff base ligands were designed and synthesized.Secondly, the synthesis methods of2,4-dihydroxyacetophenone are improved. Theresorcinol, glacial acetic acid, anhydrous zinc chloride mixed together. The mixturewas microwave-irradiated(150W) for a few minutes and than precipitated. Yield:68%.A new synthesis method of3,5-dichloro-2,4-dihydroxyacetophenone was established.The2,4-dihydroxyacetophenone, glacial acetic and HCl were dissolved in the mixture solution of ethanol followed by the addition of KClO3aqueous solution after stirringfor1h at50～60℃. Yield:76%. On this basis,4kinds of β-diketonates ligands weredesigned and synthesized. By infrared spectroscopy, elemental analysis and singlecrystal X ray diffraction analysis and other methods to characterize its structure.Thirdly,65kinds of halogen substituent salicylaldehyde Schiff basestransition-metal complexes and20kinds of β-diketonates transition-metal complexeswere synthesized by halogen substituent salicylaldehyde Schiff bases ligands,β-diketonates ligands and5kinds of transition metal salts(Cu, Co, Ni, Zn, Mn) onmicrowave solid state synthesis, respectively. The32kinds of complexes crystals areproduced. Microwave solid state synthesis conditions transition-metal complexeswere explored. By infrared spectroscopy, elemental analysis and single crystal X raydiffraction analysis and other methods to characterize its structure.Finally, Antibacterial activity of transition-metal complexes was tested against3kinds of Gram-positive bacteria and3kinds of Gram-negative bacteria. Therelationships between the structures and the antibacterial activities have been studied.Have the effect of the central ion, coordination environment of complexes andintramolecular hydrogen bond on Gram bacteria inhibition. Inhibition of coppercomplex is the best. Inhibitory effect of nickel and cobalt complex is medium.Inhibitory effect of zinc and manganese complex is the weakest. The inhibitory effectof four-coordinated complex against Gram bacteria is better than six-coordinatedcomplex. The inhibitory effect of quadrilateral coordination environment complexagainst Gram bacteria is better than tetrahedron coordination environment complex.Antibacterial activity of complexes containing intramolecular hydrogen bond againstGram bacteria is better than does not contain hydrogen bonds. Antibacterial activity ofhalogen substituent salicylaldehyde Schiff bases transition-metal complexes againstGram bacteria is better than β-diketonates transition-metal complexes.103figures,78tables,237referneces.更多还原