基于胺酚配体的3d-4f异金属配合物的构筑及性能研究

发布时间：2018-02-04 08:54

本文关键词： 单分子磁体荧光 3d-4f 多功能材料有效能垒　出处：《江西理工大学》2017年硕士论文　论文类型：学位论文

【摘要】：稀土元素具有独特的光、电、磁等理化性质,在多功能材料制备中具有重要的应用价值。一直以来大多数研究者往往将稀土配合物作为单一的功能材料使用,很少有研究者同时利用稀土离子的磁性能和荧光性能制备磁性-发光双功能分子材料。鉴于3d-4f异金属配合物磁性-发光双功能分子材料的研究还比较少,本论文选用l,1,1-三(2-氨基乙基)胺(tren)为骨架引入2-羟基-3-甲氧基苯甲醛、3-醛基水杨酸,并通过还原得到两个胺酚多齿配体(amine-phenol ligands),通过配体分割合成法构筑了9个3d-4f异金属多核配合物。通过单晶衍射仪、元素分析、红外光谱、荧光光谱、X-射线粉末衍射仪、TG以及磁性测量系统等多种表征手段,对3d-4f异金属多核配合物的结构、光谱性质和磁性能进行了详细的研究。第一章,综述了本文工作的研究背景及相关现状,简要的总结和评述了3d-4f异金属单分子磁体的研究进展、磁性-发光双功能分子材料的研究进展。结合国内外研究的相关现状,系统的阐明了本论文的选题依据以及所取得的研究进展。第二章,主要研究了以tris(((2-hydroxy-3-methoxybenzy1)amino)ethyl)amine1为配体通过双溶剂(甲醇:三氯甲烷=1:1)恒温挥发法合成了6个3d-4f异金属三核配合物[M2LnL2]·2ClO4·H2O(M=Ni,Ln=Gd(1),Tb(2),Dy(3);M=Zn,Ln=Gd(4),Tb(5),Dy(6)),并对其晶体结构、光谱性质、磁性等进行了详细的表征。单晶测试结果表明配合物1-6属于同构物,属于单斜晶系、P21/c空间群。磁性研究表明,配合物1-3中NiII与LnIII金属离子之间存在铁磁耦合作用,配合物3表现出了非常弱的场诱导慢磁弛豫行为,且具有多个磁弛豫过程。配合物5和6表现出了典型的场诱导慢磁弛豫行为且在2 K温度下的场依赖的磁化强度曲线中配合物6观察到了蝴蝶型的磁滞回线。在50 kG和2.0 K时配合物1的磁熵变达到了9.31 J kg-1K-1。荧光光谱分析表明,有机配体L3-可以作为天线配体敏化稀土离子发光,配合物3、5、6三者都具有稀土离子特征的窄带发射峰。第三章,主要通过配体分割合成法得到了3个基于胺酚多齿配体的3d-4f异金属六核配合物[Ni4Ln2(L1)4(NO3)2]·4NO3(Ln=Gd(7),Tb(8),Dy(9)),并对其晶体结构、热稳定性、磁性等进行了详细的表征。单晶测试结果表明配合物7属于三斜晶系、P-1空间群,配合物8和9属于三方晶系、R-3空间群。磁性研究表明,配合物7-9中NiII与LnIII金属离子之间存在弱铁磁耦合作用,配合物9表现出了非常弱的场诱导慢磁弛豫行为。
[Abstract]:Rare earth elements have unique physical and chemical properties, such as light, electricity, magnetic and so on, which have important application value in the preparation of multifunctional materials. Most researchers have always used rare earth complexes as a single functional material. Few researchers have made use of the magnetic properties and fluorescence properties of rare earth ions to prepare magneto-luminescent bifunctional molecular materials at the same time. . In this paper, we introduce 2-hydroxy-3-methoxybenzaldehyde 3-aldosalicylic acid as the skeleton. Two amine-phenol ligandswere obtained by reduction. Nine 3d-4f heterometallic polynuclear complexes were constructed by ligand fractionation synthesis method, which were characterized by single crystal diffractometer, elemental analysis, infrared spectrum, fluorescence spectrum and X-ray powder diffractometer. The structure, spectral properties and magnetic properties of 3d-4f heterometallic polynuclear complexes were investigated by TG and magnetic measurement system. Chapter 1. The research background and current situation of this paper are reviewed, and the research progress of 3d-4f isomeric monolayer magnets is briefly reviewed. The research progress of magnetic-luminescent bifunctional molecular materials. Combined with the current situation of domestic and foreign research, the basis of this thesis and the research progress made are systematically expounded. Chapter 2. The use of tris(((2-hydroxy-3-methoxybenzy1)amino)ethyl)amine1 as ligand was studied in this paper. Synthesis of six 3d-4f heterometallic trinuclear complexes by isothermal volatilization with methanol: trichloromethane 1: 1). [M _ 2LnL _ 2] 路2ClO _ 4 路H _ 2O _ 2; The crystal structure and spectral properties of MZZN LnGdC4, TbC5 and Dy6 are also discussed in this paper, and their crystal structure and spectral properties are also discussed in this paper, and the crystal structure and spectral properties are also discussed in this paper. The results of single crystal test show that the complex 1-6 belongs to isomorphism and belongs to the monoclinic system P21 / c space group. The magnetic study shows that the complex 1-6 belongs to the isomorphism group and belongs to the monoclinic system P21 / c space group. Ferromagnetic coupling exists between NiII and LnIII metal ions in complexes 1-3, and complex 3 exhibits very weak field-induced slow magnetic relaxation behavior. The complexes 5 and 6 exhibit typical field-induced slow magnetic relaxation behavior. In the field-dependent magnetization curve at K temperature, the hysteresis loop of butterfly type was observed in complex 6. The magnetic entropy of complex 1 reached 9.31 J at 50 KG and 2.0 K. Kg-1K-1. fluorescence spectrum analysis showed that. Organic ligands L3- can be used as antenna ligands to sensitize the luminescence of rare earth ions. Three 3-d-4f hexaduclear heterometallic complexes based on polydentate ligands of aminophenol were synthesized by ligand partitioning synthesis. [The crystal structure and thermal stability of Ni4Ln2(L1)4(NO3)2 were studied. The magnetic properties were characterized in detail. The results of single crystal test showed that the complex 7 belongs to the trichroic crystal system and the complexes 8 and 9 belong to the rhombohedral crystal system R-3 space group. The magnetic study shows that the complex 7 belongs to the trichroic crystal system. There is a weak ferromagnetic coupling between NiII and LnIII metal ions in complex 7-9, and complex 9 exhibits very weak field-induced slow magnetic relaxation behavior.
【学位授予单位】：江西理工大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O641.4

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