【作者】 劳雁妮；

【导师】 杨仕平；

【作者基本信息】 上海师范大学 ， 应用化学， 2009， 硕士

【摘要】 在本论文中,成功合成了三种新颖的含二氢咪唑基的配体:1,3-二(4,5-二氢-1H-咪唑-2-基)苯(m-Bib),1,4-二(4,5-二氢-1H-咪唑-2-基)苯(p-Bib), 9,10-二氢苯并[反]咪唑并[2,1-а]异喹啉-7-酮(Bio)及它们的配合物[(H2Bib) (NO3)2] 1, [Cu2 (OBib)] (COOCH3)2(OCH3) 2, [Cu2(OBib)2] (COOCH3)2(OCH3) (H2O) 3, [Cu2(Bib)2 (COOCH3)∞(H2O)∞4, [Co(CN)6]·H2Bib·2H2O 5, [Cu4Cl10O] (Bib)2 6, [Cu4Cl10 O]·(H2p -Bib)2 (CH3CH2OH) 7, [Cu2(Bio)Cl3](Bio) 8, (Bio)2CuCl4 9, [Cu(Bio)2Cl2] 10, [Cu(Bio)2 (NO3)2] 11, [HBio·NO3] 12, [Eu2(isophth)3(H2O)2]n 13, [Tb2 (isophth)3 (H2O)2]n 14,(H2isophth=间苯二甲酸),并用EA、IR、UV、X-射线单晶衍射、ESR、ESI、磁性、荧光进行了表征。具体内容如下:第一章概述了本文的研究背景。第二章第一节描述了以Bib、p-Bib为配体的金属铜配合物的合成方法及X-射线晶体衍射、红外、紫外、电子顺磁共振及磁性质的研究。单晶结构分析表明,1、5-7是非共价配合物,由对应配体与阴离子通过氢键形成的2-D、3-D网络; 2、3均为双核铜配合物,结构为顺反异构,配体苯环的碳氢键被氧化, Cu(II)处于平面四边形结构;4呈多核链状,金属离子处在变形的四面体配位环境中,通过氢键及弱相互作用形成二维到三维结构,磁性研究表明这三种铜配合物均显示出反铁磁性。第二节介绍了由Bio配体得到的配位化合物的合成方法及X-射线晶体衍射,红外、元素分析及电子顺磁共振的研究,配位聚合物8、10、11均呈现单核结构,在配合物8中铜离子处在变形的四面体配位环境中,而10和11的铜离子均处在平面四边形的配位环境中,9和12是非共价配合物,它们都通过氢键及弱相互作用形成二维到三维结构。第三节介绍了由Bib配体采用水热法合成稀土金属配合物分子体系,得到了稀土与间苯二甲酸配合物13和14。X射线单晶衍射表明,两个稀土离子处于不同的配位环境中,Eu(1)和Tb(1)离子分别处于9配位的五角双锥和8配位双帽三棱柱配位构型,而Eu(2)和Tb(2)则处于7配位的单帽四方棱柱构型。荧光测试结果表明,二者呈现出较好的荧光性能。更多还原

【Abstract】 In this thesis, a series of novel complexes [(H2Bib) (NO3)2] 1, [Cu2 (OBib)] (COOCH3)2(OCH3) 2, [Cu2(OBib)2] (COOCH3)2(OCH3) (H2O) 3, [Cu2(Bib)2 (COOCH3)∞(H2O)∞4, [Co(CN)6]·H2Bib·2H2O 5, [Cu4Cl10O] (Bib)2 6, [Cu4Cl10 O]·(H2p -Bib)2 (CH3CH2OH) 7, [Cu2(Bio)Cl3](Bio) 8, (Bio)2CuCl4 9, [Cu(Bio)2Cl2] 10, [Cu(Bio)2 (NO3)2] 11, [HBio·NO3] 12, [Eu2(isophth)3(H2O)2]n 13, [Tb2 (isophth)3 (H2O)2]n 14, (H2isophth=1,3-benzendiicarboxylic acid), have been firstly synthesized with Bib=1, 3- bis (4, 5-dihydro-1H-imidazol-2-yl) benzene, p-Bib=1, 4-bis (4, 5-dihydro-1H-imidazol-2-yl) benzene, Bio=9, 10-dihydro-benzo [de] imidazo [2, 1-a] isoquinolin-7-one, respectively, and characterized by elemental analysis, infrared spectroscopy, Uv-vis spectroscopy, variable temperature susceptibility and magnetism. The thesis consists of following two parts:In the first chapter, the background of this research is concisely introduced.In the first period of the second chapter, we described the preparation and the characteristics, by x-ray crystallgrapy, IR, UV/Vis, magnetism, ESR, ESI and magnetism for the Cu- Bib or Cu- p-Bib complexes. 1 and 5- 7 were the nonconvalent production, forming the 2-D or 3-D net through H-bonds. 2 and 3 showed the Cis-trans isomers of dinuclear-copper structures. The ligands were oxidated and C-H bonds were activated and Cu(II) was coordinated with four atoms in a quadrangle geometry. The compound 4 was a single chain, where the metal ion was in a distorted tetrahedron gemetry. They formed 2-D or 3-D structure by H-bond or weak interaction. They showed ferromagnetic properties.In the second period, the Cu-bio and bio complexes had been synthesized and charactered by x--ray crystallgrapy, IR, ESR. Complexes 8、10、11 were mononuclear structures. In the compound 8, Cu ion was coordinated in a distorted tetrahedron geometry, but in complexes 10 and 11, the Cu ions were in a in a quadrangle geometry. 9 and 12 are the nonconvalent production. All they formed 2-D or 3-D structure by H-bond or weak interaction.In the third period, two Eu3+ and Tb3+ complexes with 1, 3-bis (4,5-dihydro-1H- imidazol-2-yl) benzene by hydrothermal assembly have been synthesized through the reaction of Eu3+ and Tb3+ salts with Bib. X-ray single-crystal diffraction revealed that the both Eu3+ complexes 13 and Tb3+ complexes 14 displayed the monoclinic crystal system .The two Eu3+ atoms of 13 were coordinated by seven and nine atoms in a pentagonal bipyramid geometry and a distorted capped square prism geometry while two Tb3+ atoms of 14 were lignated with seven and eight atoms in a pentagonal bipyramid geometry and a two-distorted capped triple prism geometry. The emission spectra of the Eu3+ and Tb3+ complexes indicated that they had excellent luminescence properties.更多还原