氮氧自由基金属功能配合物的组装

发布时间：2018-06-09 03:27

本文选题：氮氧自由基 + 稀土金属　；参考：《天津科技大学》2015年硕士论文

【摘要】：分子基材料是磁性材料研究的一个重要分支。在分子基材料研究领域中,金属-自由基方法是设计和合成磁性分子材料的一条有效的途径。本论文通过对氮氧自由基-金属功能配合物的设计和组装,成功合成出21个氮氧自由基-金属配合物,并且对这些配合物进行元素分析,红外光谱,紫外-可见光谱,荧光光谱,热重等表征,并对化合物的晶体结构、磁学性质和抑菌活性进行了研究。本文主要研究内容如下：合成了8种氮氧自由基,分别为3-甲基噻吩基氮氧自由基,3-苄氧基氮氧自由基,双自由基,对溴基苯基氮氧自由基,对氟基苯基氮氧自由基,对二甲氨基苯基氮氧自由基,对羧基苯基氮氧自由基,4-吡啶氮氧自由基和4种草酰胺大环化合物。以3-甲基噻吩基自由基为有机配体与稀土,过渡金属六氟乙酰丙酮盐进行反应得到8个配合物,并且对其中的两个配合物Dy(hfac)3(NITTh-m-CH3)2和Tb(hfac)3(NITTh-m-CH3)2进行了X-射线单晶衍射测试,结果表明：两个配合物都是三斜晶系,具有八配位的畸形十二面体,分子间通过三个氢键作用,形成三维的网状结构。以3-苄氧基苯基自由基为有机配体与稀土,过渡金属六氟乙酰丙酮盐进行反应得到7个配合物,并且对其中的一个配合物Cu3(hfac)6(NITPh-m-OCH2-Ph)2进行了X-射线单晶衍射测试,它是三核配合物、三斜晶系,中心离子铜与来自于六氟乙酰丙酮的四个氧原子和自由基的一个氧原子形成五配位化合物,分子间不存在氢键。以对二甲氨基苯基氮氧自由基,对氟基苯基氮氧自由基和对溴基苯基氮氧自由基为有机配体与稀土金属六氟乙酰丙酮盐进行反应得到6个配合物,分别对这6个配合物进行了磁性测试,结果显示这六个配合物中金属离子与自由基之间都存在一定的弱磁相互作用。探究稀土氯化物,氮氧自由基配体和稀土-自由基配合物对酵母菌,金黄色葡萄球菌和大肠杆菌的抑菌性能。利用滤纸条扩散法测试其抑菌圈直径的大小来衡量抑菌性能的强弱。得出稀土配合物具有较强的抑菌效果,浓度越高则其抑菌性能越好,同一浓度下镝系列的配合物对菌种的抑菌性能较好,这或许和配合物的磁性有关。这些为设计、合成和应用稀土金属-自由基分子材料提供了很好的科学依据。
[Abstract]:Molecular-based materials are an important branch of magnetic materials. In the field of molecular-based materials, metal-free radical method is an effective way to design and synthesize magnetic molecular materials. In this paper, 21 nitroxy-metal complexes were successfully synthesized by the design and assembly of functional complexes of nitroxyl radicals and metals. The complexes were characterized by elemental analysis, IR and UV-Vis spectra. The crystal structure, magnetic properties and bacteriostatic activity of the compounds were studied. The main contents of this paper are as follows: eight kinds of nitroxyl radicals were synthesized, which were 3-methylthiophenyl nitroxyl radical, double radical, p-bromophenyl nitroxyl radical, p-fluorophenyl nitroxyl radical. P-dimethylaminophenyl nitroxyl radical, p-carboxyphenyl nitroxyl radical, 4-pyridine nitroxyl radical and four oxalamide macrocyclic compounds. Eight complexes of transition metal hexafluoroacetylacetone salt were synthesized by using 3-methylthiophene radical as organic ligands and rare earths. Two of the complexes Dyhfaco _ 3NITTh-m-Ch _ 3H _ 2 and Tbbhfaco _ 3N _ IT-Th-m-Ch _ 3H _ 2 were characterized by X-ray single crystal diffraction. The results show that the two complexes are tridiagonal and have eight coordination deformed dodecahedrons. Seven complexes of transition metal hexafluoroacetylacetone salt were synthesized by using 3-benzoxy phenyl radical as organic ligand and rare earth. One of the complexes, Cu _ 3H _ 2O _ 6N _ ITPh-m-OCH _ 2-Pho _ 2, was characterized by X-ray single crystal diffraction, which is a trinuclear complex. In the triclinic system, the central ion copper forms a five-coordination compound with four oxygen atoms from hexafluoroacetylacetone and one oxygen atom from free radical, and there is no hydrogen bond between them. Six complexes were synthesized by the reaction of p-dimethylaminophenyl nitroxyl radical, p-fluorophenyl nitroxyl radical and p-bromophenyl nitroxyl radical with rare earth metal hexafluoroacetylacetone. The magnetic properties of the six complexes were tested, and the results showed that there was a weak magnetic interaction between metal ions and free radicals in the six complexes. To investigate the antibacterial properties of rare earth chloride, nitroxyl radical ligands and rare earth radical complexes against yeast, Staphylococcus aureus and Escherichia coli. The diameter of the bacteriostasis circle was measured by the filter strip diffusion method to measure the bacteriostatic performance. The results showed that the rare earth complexes had strong bacteriostatic effect, and the higher the concentration, the better the bacteriostatic performance of dysprosium complexes, which might be related to the magnetic properties of the complexes. These provide a good scientific basis for the design, synthesis and application of rare earth metal-free radical molecular materials.
【学位授予单位】：天津科技大学
【学位级别】：硕士
【学位授予年份】：2015
【分类号】：O641.4

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