【作者】 那勃；

【导师】 程鹏；

【作者基本信息】 南开大学 ， 无机化学， 2013， 博士

【摘要】 本论文采用异烟酸氮氧化物(HINO)、5-羟基烟酸(H2NA)和4-吡啶硫代乙酸(HPA)三个吡啶羧酸类配体,与稀土金属离子反应,合成了23个新颖的稀土金属配合物。采用单晶结构解析、元素分析、X-射线粉末衍射及原子发射光谱等测试方法对所合成的配合物进行了结构表征,并详细研究了其磁学性质。以异烟酸氮氧化物为配体,与镝离子反应,得到了一系列以双核镝为构筑单元的三维框架结构配合物。通过对孔道中客体溶剂分子的调控,使其展现出了不同的磁行为。CONDON软件计算结果表明其不同磁行为来源于体系内双核镝单元之间铁磁相互作用大小的改变,这是首例具有溶剂分子磁响应现象的三维稀土配合物,且均显示了磁化强度慢磁弛豫行为。用5-羟基烟酸作为配体,通过水热方法合成了一系列六配位稀土配合物,这是首例在纯水溶剂中合成的稳定的二维六配位稀土配合物。通过对钇稀释之后的镝配合物样品磁性数据进行分析,证实其慢磁弛豫行为主要由镝离子的单离子磁各向异性导致,为新型单离子磁体的设计与合成提供了新的思路。采用4-吡啶硫代乙酸为配体,得到了一系列具有极性空间群的一维链状稀土配合物,其中镝配合物在直流外磁场的存在下展示出了慢磁弛豫行为。更多还原

【Abstract】 Based on ligands of isonicotinic acid N-oxide (HINO),5-hydroxynicotinic acid (H2NA) and (4-pyridylthio)acetic acid (HPA),23new lanthanide complexes have been synthesized, whose structures and properties were characterized by elemental analysis, powder X-ray diffraction, ICP-AES, direct-current (dc) magnetic susceptibilities and alternating-current (ac) magnetic susceptibilities.A series of3D framework complexes were obtained with DyⅢ ions, HINO and corresponding solvents. Magnetic properties of these complexes were affected by the type of guest solvents, as illustrated by magnetic measurements. The variation of magnetic properties mainly came from the change of the ferromagnetic interaction between dinuclear dysprosium units due to the calculation results through program CONDON. This is the first observation of lanthanide framework complexes exhibiting magnetic response and slow relaxtion of magnetization toward solvent molecules. Unusual hexa-coordinated lanthanide complexes with H2NA as ligand have been obtained and structurally characterized by hydrothermal method, which show the first examples for syntheses of such stable complexes from water solution. Interesting superparamagnetic behavior was observed from these2D complexes, and the results of calculation and Y-diluted experiments confirmed that the slow relaxation of the magnetization originated from the single-ion anisotropy of DyⅢ ions. A series of new HPA ligated complexes containing polar space group and1D lanthanide chains were synthesized and characterized, the Dy complex showed slow relaxation of magnetization under the given dc field.更多还原