含氮杂环羧酸类配体的配合物结构及其性能研究
发布时间：2018-11-18 08:56
【摘要】：功能配合物因具有可控的结构及独特的优良性能,已在光、电、磁、生物医学等领域呈现出潜在的应用价值,目前化学家们研究的重点在于设计合成具有特定功能的配合物。经过大量的理论研究及实验结果显示,配合物的功能与其结构有着必然的联系,因此如何调控配合物的结构进而调控其功能已成为当前配位化学家们研究的热点之一。在功能配合物中,有机配体与金属离子由于受实验条件等多种因素影响可形成一系列具有新颖独特结构及优良性能的配合物,故选取适合的有机配体就变得至关重要。近些年来,含氮杂环羧酸类配体备受关注,此类配体同时兼具了氮杂环和羧酸配体丰富多彩的配位方式和功能性,故更有利于构筑新型的功能配合物。为了探究影响配合物结构的主要因素及其结构与功能之间的相互关系,本文设计合成了一类结构各异的含氮杂环羧酸类配体,通过将其与不同的金属离子配位,构筑了8个具有新颖结构的功能配合物,分别为:Cu(DPPA)Cl(1),Mn(H2IDC)2(H2O)2(2),Cu2(TMBA)4(CH3OH)2(3),Mn(CPBm)2(H2O)4(4),Ni(CPBm)2(CH3OH)2(5),Co(CPBm)2(6)(7),Ni(CPBm)2(8),并利用X-射线单晶衍射表征了它们的结构。其中配合物(1)为单核结构;配合物(2)为氢键构筑的三维网络;配合物(3)中的双核结构单元通过氢键连接,形成了一维的链状结构;配合物(4)通过4个不同方向的氢键连接形成了三维氢键网络;配合物(5)是具有44拓扑网络的二维层状结构,每个二维层相互平行堆积又构成三维网络结构;配合物(6)(7)(8)具有相似的二维层状结构及一维孔道结构。此外,利用X-射线粉末衍射(PXRD)和热重分析法(TGA)对所得配合物的相纯度和热稳定性进行了测试,同时对部分配合物进行了荧光、气体吸附和电化学储锂性能的研究。研究结果显示,配合物(1)在303nm激发下,在363nm处有一个较强的荧光发射峰;配合物(7)属于介孔材料,BET比表面积和Langmuir比表面积分别为34.42m2/g和73.62m2/g,另外,配合物(7)作为锂离子电池的负极材料具有优异的倍率性能和循环稳定性能,有望成为一种新型的锂离子电池电极材料。
[Abstract]:Functional complexes have shown potential applications in light, electricity, magnetism, biomedicine and other fields because of their controllable structure and unique excellent properties. At present, the focus of chemists is to design and synthesize complexes with specific functions. A large number of theoretical studies and experimental results show that the functions of the complexes have an inevitable relationship with their structures. Therefore, how to regulate the structure of complexes and then their functions has become one of the hot topics of coordination chemists. In the functional complexes, organic ligands and metal ions can form a series of complexes with novel and unique structures and excellent properties because of the influence of experimental conditions, so it is very important to select suitable organic ligands. In recent years, nitrogen-containing heterocyclic carboxylic acid ligands have attracted much attention. These ligands have both rich and colorful coordination modes and functions of nitrogen heterocyclic and carboxylic acid ligands, so they are more conducive to the construction of new functional complexes. In order to investigate the main factors affecting the structure of the complexes and the relationship between their structure and function, a class of heterocyclic carboxylic acid ligands with different structures were designed and synthesized, which were coordinated with different metal ions. Eight novel functional complexes,: Cu (DPPA) Cl (_ 1), Mn (H2IDC) _ 2 (H _ 2O) _ 2 (2), Cu2 (TMBA) _ 4 (CH3OH) _ 2 (3), Mn (CPBm) _ 2 (H _ 2O) _ 4 (4), were constructed. Ni (CPBm) _ 2 (CH3OH) _ 2 (5), Co (CPBm) _ 2 (6) (7), Ni (CPBm) _ 2 (8) were characterized by X-ray single crystal diffraction. The complex (1) is a mononuclear structure, the complex (2) is a three-dimensional network constructed by hydrogen bonds, and the binuclear structure units in the complex (3) are connected by hydrogen bonds to form a one-dimensional chain structure. The complex (4) forms a three-dimensional hydrogen bond network through four hydrogen bonds in different directions, and the complex (5) is a two-dimensional layered structure with 44 topological networks, each of which is stacked in parallel with each other to form a three-dimensional network structure. Complex (6) (7) (8) has similar two-dimensional layered structure and one-dimensional pore structure. In addition, the phase purity and thermal stability of the complexes were tested by X-ray powder diffraction (PXRD) and thermogravimetric analysis (TGA). The fluorescence, gas adsorption and electrochemical lithium-storage properties of some complexes were also studied. The results show that complex (1) has a strong fluorescence emission peak at 363nm under the excitation of 303nm; Complexes (7) belong to mesoporous materials, the specific surface area of BET and Langmuir are 34.42m2/g and 73.62 m2 / g, respectively. In addition, the complex (7) has excellent rate performance and cyclic stability as anode materials for lithium ion batteries. It is expected to be a new electrode material for lithium ion batteries.
【学位授予单位】：哈尔滨工业大学
【学位级别】：硕士
【学位授予年份】：2016
【分类号】：O641.4
，
本文编号：2339546
[Abstract]:Functional complexes have shown potential applications in light, electricity, magnetism, biomedicine and other fields because of their controllable structure and unique excellent properties. At present, the focus of chemists is to design and synthesize complexes with specific functions. A large number of theoretical studies and experimental results show that the functions of the complexes have an inevitable relationship with their structures. Therefore, how to regulate the structure of complexes and then their functions has become one of the hot topics of coordination chemists. In the functional complexes, organic ligands and metal ions can form a series of complexes with novel and unique structures and excellent properties because of the influence of experimental conditions, so it is very important to select suitable organic ligands. In recent years, nitrogen-containing heterocyclic carboxylic acid ligands have attracted much attention. These ligands have both rich and colorful coordination modes and functions of nitrogen heterocyclic and carboxylic acid ligands, so they are more conducive to the construction of new functional complexes. In order to investigate the main factors affecting the structure of the complexes and the relationship between their structure and function, a class of heterocyclic carboxylic acid ligands with different structures were designed and synthesized, which were coordinated with different metal ions. Eight novel functional complexes,: Cu (DPPA) Cl (_ 1), Mn (H2IDC) _ 2 (H _ 2O) _ 2 (2), Cu2 (TMBA) _ 4 (CH3OH) _ 2 (3), Mn (CPBm) _ 2 (H _ 2O) _ 4 (4), were constructed. Ni (CPBm) _ 2 (CH3OH) _ 2 (5), Co (CPBm) _ 2 (6) (7), Ni (CPBm) _ 2 (8) were characterized by X-ray single crystal diffraction. The complex (1) is a mononuclear structure, the complex (2) is a three-dimensional network constructed by hydrogen bonds, and the binuclear structure units in the complex (3) are connected by hydrogen bonds to form a one-dimensional chain structure. The complex (4) forms a three-dimensional hydrogen bond network through four hydrogen bonds in different directions, and the complex (5) is a two-dimensional layered structure with 44 topological networks, each of which is stacked in parallel with each other to form a three-dimensional network structure. Complex (6) (7) (8) has similar two-dimensional layered structure and one-dimensional pore structure. In addition, the phase purity and thermal stability of the complexes were tested by X-ray powder diffraction (PXRD) and thermogravimetric analysis (TGA). The fluorescence, gas adsorption and electrochemical lithium-storage properties of some complexes were also studied. The results show that complex (1) has a strong fluorescence emission peak at 363nm under the excitation of 303nm; Complexes (7) belong to mesoporous materials, the specific surface area of BET and Langmuir are 34.42m2/g and 73.62 m2 / g, respectively. In addition, the complex (7) has excellent rate performance and cyclic stability as anode materials for lithium ion batteries. It is expected to be a new electrode material for lithium ion batteries.
【学位授予单位】：哈尔滨工业大学
【学位级别】：硕士
【学位授予年份】：2016
【分类号】：O641.4
，
本文编号：2339546
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