【作者】 李付安；

【导师】 陶偌偈；

【作者基本信息】 河南大学 ， 无机化学， 2005， 硕士

【摘要】 二十多年来,分子基磁材料显示出了广阔的发展前景,异金属双核配合物的研究在该领域起着重要和主导作用。大量的异金属双核配合物得到了合成,磁性得到了研究。近期来,不同顺磁中心之间磁交换的研究已成为磁学领域的热点,而有目的获得异多核配合物的有效方法是以“配合物作配体” 的方法。这些阴离子母体特别适合于设计异金属配合物,并在分子磁体的发展中起着重要的作用。羧基、酚氧基和酰胺基是优良的多功能基团,它们既能螯合,又能桥连以形成结构新奇的多核配合物或超分子配位化合物,在磁学研究中具有一定意义。 鉴于以上原因和分子设计的观点,本文设计并合成了含有羧基、酚氧基的酰胺类Schiff碱的单核、异三核配合物和多核配位聚合物以及不对称双Schiff碱单核、三核配合物,并对其进行了结构表征和性质研究。主要内容如下: （1）利用酯类化合物的胺解反应,将乙二胺与水杨酸乙酯混合反应得到了 1:1 的单缩产物——1-（2-羟基苯甲酰胺）-2-氨基乙烷;通过该产物与三羧基水杨醛反应得到了含有酚氧基和羧基的酰胺类Schiff碱配体N-（3-羧基水杨醛）-N’-（2-羟基苯甲酸乙酯）缩乙二胺（H₄L）。利用该配体（H₄L）,我们合成了含有负二价配阴离子的铜单核配位化合物（K₂CuL·1.5H₂O）和镍单核配位化合物（K₂NiL·H₂O）,并用IR 谱、元素分析、热分析等手段对其进行了表征和性质研究。 通过铜单核配合物（K₂CuL·1.5H₂O）和二价过渡金属醋酸盐[M（OAC）₂·nH₂O]（M=Mn、Co、Cu、Zn） 的甲醇溶液反应,得到了一系列的多核配位聚合物,用X-射线衍射方法测定了它们的晶体结构,并进行了性质研究。结构解析表明,该系列的多核配合物均为由两种四核环交替排列构成的 1D 链状结构的配位聚合物。在 5-300K 温度范围内,测定了该系列配位聚合物的变温磁化率,经拟合得到了Cu-Mn、Cu-Co、Cu-Cu 多核配合物磁参数,其中 J 分别为-49.3、-26.8 和-130.5cm-1,表明该系列多核配合物金属离子间的磁交换均为反铁磁交换作用（J<0）,且这种作用不是很强（∣J∣不很大）。更多还原

【Abstract】 The molecular-based magnetic materials have shown spectacular advances over the past two decades, in which the study of heterometallic binuclear complexes has played an important and leading role. A number of heterometallic binuclear complexes have been synthesized and their magnetic properties have been investingated. It is well known that the magnetic interactions between two nonequivalent paramagnetic centers may lead to situations that cannot be encountered in species containing only one kind of center. A successful strategy in obtaining the desired spin topology is the “complex as ligand” approach. These anionic precursors are particularly suitable for designing heterometallic complexes and have played an important role in the development of molecular magnetism. Acylamino-Schiff bases containing phenol-oxygen groups and amido group are good versatile organic ligands, which can chelate as well as bridge metal ions to construct discrete and extended structures, further forming 1D, 2D or 3D structure polymers with infinitely extended chain structure. They should play an important for the study of magnetic property. In view of reasons above and from the standpoint of molecular design, we have designed and synthesized asymmetrical mononuclear、heterotrinuclear complexes and heterometal polymers of acylamino-Schiff bases containing phenol-oxygen groups and mononuclear 、heterotrinuclear complexes of asymmetrical double Schiff base. These compounds were characterized by single-crystal X-ray analysis and executed properties study. The main contents are described as following: （1） According to the principle of ester aminolysis, we have prepared the compound [N-（2-Hydroxybenzamido）-N’-（2-amino）ethane] by ethyl salicylate and ethylene- diamine mixed and refluxed at 110°C. Asymmetrical acylamino-Schiff base ligand H4L containing phenol-oxygen groups was also obtained by 3-Carboxylsalicylidene and N-（2-Hydroxybenzamido）-N’-（2-amino）ethane refluxed in ethanol. Further, we synthesized copper mononuclear complex（K₂CuL）and nickel mononuclear complex（K₂NiL） by the ligand H₄L and Copper（II） acetate monohydrate （or nickel（II） acetate tetrahydrate） refluxed in ethanol. These compounds were characterized and investingated by IR Spectra, elemental analyses and thermogravimetric analyses et al. A series of heterometal complexes have been designed and synthesized by copper mononuclear complex（K₂CuL）and d-transition metal ions M²⁺ self-assembly in methanol at room temperature and their UV-Vis spectra, IR spectra, thermal properties and magnetic Properties et al. have been studied. Their crystal structures have been determined by X-ray analysis. These heterometal complexes are 1D infinite chain-structure polymers, there are unnumber cyclic tetranuclear structure in every chain, the tetranuclear cyclic have two different sorts of structures, are arrayed alternately and constructed these long molecules chain. The variable magnetic properties of these polymers have been determined in the temperature range 5³00K, which indicate that the interaction between the metal ions is antiferromagnetical. The magnetic susceptibility was analyzed by eq derived from the approximate modal[1²] previously reported and obtained satisfactory result. When substituting copper mononuclear complex （K₂NiL） for nickel mononuclear complex （K₂CuL） above the reaction, a series of heterometal polymers are also obtained. Because square planar nickel complexes are of diamagnetism, their properties have been investingated except for magnetic properties, Their crystal structures have been determined by X-ray analysis, which they have approximate structure with the former. （2）Asymmetrical acylamino-Schiff base ligand H3CSe （figure（b）） containing phenol-oxygen groups was also obtained by 5-chlorosalicylaldehyde and N-（2-Hydroxybenzamido）-N’-（2-amino）ethane refluxed in ethanol. Further, we synthesized copper mononuclear complex（KCuCSe）by the ligand H₃CSe and Copper（II） acetate monohydrate refluxed in ethanol. Two sorts of cis-heterometal triunclear complex更多还原