【作者】 常岭；

【导师】 于兆文；

【作者基本信息】 河南大学 ， 无机化学， 2009， 硕士

【摘要】 Schiff碱及其金属配合物一直是化学学科研究的热点之一。主要在于它们所含C=N基团的电子效应、与中心离子的配位作用以及功能性等因素。它们可用作鳌合剂、催化剂、稳定剂和生物活性剂等。Schiff碱在国内外已经进行了大量的研究和报道,但是邻硝基苯胺类Schiff碱当前在国内外研究的却比较少。基于此,我们考虑对邻硝基苯胺类Schiff碱及其配合物进行研究。同时,我们也对研究较多的salen型Schiff碱配合物也进行了一些研究。本文设计合成了3-羧基水杨醛的邻硝基苯胺Schiff碱和salen型Schiff碱,同时对这些化合物进行了结构表征和性质研究,主要内容如下:（1）以3-羧基水杨醛缩邻硝基苯胺Schiff碱H₂CHNA为配体,合成了双核配合物[Co₂（CHNA）₂],用IR光谱,荧光光谱和X射线单晶衍射对其结构进行了表征。结果表明该晶体属于单斜晶系,P2₁/c空间群,晶胞参数:a=0.83398（6）nm,b=1.10454（8）nm,c=1.3368l（9）nm,α=90.00°,β=99.6040（10）°,γ=90.00°,Z=2,R₁=0.0449,wR₂=0.1113,钴离子是六配位,两个钴离子在分子中通过配体的两个酚氧原子桥连,钴离子处于变形八面体的配位几何结构中。（2）以水杨醛缩邻硝基苯胺Schiff碱H₂SANA为配体,合成了单核配合物Cu（SANA）₂,用IR光谱,荧光光谱和X射线单晶衍射对其结构进行了表征。结果表明,该晶体属于三斜晶系,P-1空间群,晶胞参数a=0.73179（14）nm,b=1.0928（2）nm,c=1.5505（3）nm,α=81.616（4）°,β=81.966（4）°,γ=74.171（4）°,Z=2,R₁=0.0683,wR₂=0.1628。铜离子为四配位,分别与两个配体的两个酚氧原子和两个C=N的氮原子配位,铜离子处于平行四边形的配位环境之中,处于四边形对角线的交点位置,故此分子呈现出高度中心对称结构。（3）合成了配体水杨醛缩邻苯二胺Schiff碱H₂OS,用IR光谱,核磁共振和X射线单晶衍射对其结构进行了表征。结果表明,该晶体属于单斜晶系,P2₁/c空间群,晶胞参数a=0.59808（5）nm,b=1.65765（14）nm,c=1.63651（15）nm,α=90°,β=91.487°,γ=90°,Z=4,R₁=0.0415,wR₂=0.1140。得到的Schiff碱中酚羟基所在的两个苯环不在一个平面,夹角为49.964（98）°，这两个苯环与邻苯二胺苯环的夹角分别为3.460（82）°和57.081（138）°。（4）以水杨醛缩邻苯二胺Schiff碱H₂OS为配体,合成了单核配合物Sn（OS）·Cl₂,用IR光谱,荧光光谱和X射线单晶衍射对其结构进行了表征。结果表明,该晶体属于三斜晶系,P-1空间群,晶胞参数a=0.75333（4）nm,b=0.98398（5）nm,c=1.26177（7）nm,α=96.4060（10）°,β=94.6070（10）°,γ=102.8400（10）°,Z=2，R₁=0.0270,wR₂=0.0669。锡原子为六配位,处于八面体的配位环境中。（5）以水杨醛缩邻苯二胺Schiff碱H₂OS为配体,合成了单核配合物Ni（OS）,用IR光谱,荧光光谱和X射线单晶衍射对其结构进行了表征。结果表明,该晶体属于正交晶系,P2₁2₁ 2₁空间群,晶体参数a=0.54649（8）nm,b=1.6588r2)nm,c=1.7281（2）nm,α=90°,β=90°,γ=90°,Z=4,R₁=0.0246,wR₂=0.0551。镍原子为四配位,处于四边形的配位环境中,镍原子仅偏离四个配位原子O1,O2,N1和N2的最小二乘平面0.71pm.（6）合成了配合物[Cu（phen）₂Cl]·ClO₄·H₂O（其中phen为邻菲咯啉）,单斜晶系,P2₁/n空间群,晶胞参数a=1.18086（8）nm,b=1.52855（10）nm,c=1.29572（9）nm,α=90°,β=93.1770（10）°,γ=90°,V=2.3352（3）nm³,Z=4,R₁=0.0481,wR₂=0.1424。Cu原子位于三角双锥的配位环境中。（7）合成了邻菲咯啉·3-羧基水杨醛·铜三元配合物[Cu（C₈H₄O₄,）(C₁₂H₈N₂)（H₂O）]（CH₃）₂NCHO,三斜晶系,P-1空间群,a=0.96936（6）nm,b=1.09020（12）nm,c=1.12800（7）nm,α=103.8340（10）°,β=109.7640（10）°,γ=98.6040（10）°,Z=2,R₁=0.0360,wR₂=0.1108。Cu原子处于轻微变形的四方锥场底心,底面被两个O原子和两个N原子占据,水分子中的O原子位于锥顶。更多还原

【Abstract】 Schiff bases and their metallic complexes have been widely investigated for more than a century. These complexes have been known for their biological activity and catalytic activity. The preface of this thesis introduces the recent advances in the synthesis and applications of Schiff base and their complexes. They have potential applications as antibacterial reagents, antiviral reagents, anticancer reagents and enzyme inhibitors, etc. Schiff base complexes have been extensively investigated at home and abroad, but the research on 2-nitroaniline Schiff bases is rare, so we synthesized and studied the 2-nitroaniline Schiff bases and their complexes. Moreover, we have also investigated the salen Schiff base complexes.In this paper, we designed and synthesized 2-nitroaniline Schiff base complexes and salen Schiff base complexes. These compounds were characterized by single-crystal X-ray analysis, ¹H NMR, IR, UV-vis, TG, etc. The main contents are described as follows:（1） Schiff base complex [Co₂（CHNA）₂], where H₂CHNA is N-（3-carboxylsalicy-lidene）-2-nitroaniline, was synthesized and characterized by IR spectrum, fluorescence spectrum and single-crystal analysis. The crystal belongs to monoclinic system, space group P2₁/c, crystal parameter: a = 0.83398（6） nm, b = 1.10454（8） nm,c= 1.33681（9） nm,α=90.00°,β=99.6040（10）°,γ=90.00°,Z=2,R₁=0.0449,wR₂=0.1113. In the molecular unit, the Co（Ⅱ） ions are bridged by two phenolate oxygen atoms of the ligands. Each metal centre has a distorted octahedral geometry.（2） Schiff base complex Cu（SANA）₂, where H₂SANA is N-salicylidene-2-nitroaniline, was synthesized and characterized by IR spectrum, fluorescence spectrum and single-crystal analysis. The crystal belongs to triclinic system, space group P-1, crystal parameter: a=0.73179（14）nm,b=1.0928（2）nm,c=1.5505（3）nm,α=81.616（4）°,β=81.966（4）°,γ=74.171（4）°,Z=2,R₁=0.0683,wR₂=0.1628. The copper（Ⅱ） ion is tetracoordinated in a parallelogram geometry, with the ligands acting as bidentate NO-chelators.（3） Schiff base ligand H₂OS, N,N’-bis（salicylidene）-o-phenylenediamine, was synthesized and characterized by IR spectrum, ¹H NMR and single-crystal analysis. The crystal belongs to monoclinic system, space group P2₁c, crystal parameter: a=0.59808（5）nm,b=1.65765（14）nm,c=1.63651（15）nm,α=90°,β=91.487°,γ=90°,Z=4,R₁=0.0415,wR₂=0.1140.（4） Schiff base complex Sn（OS）·Cl₂, where H₂OS is N,N’-bis（salicylidene）-o-phenylenediamine, was synthesized and characterized by IR spectrum, fluorescence spectrum and single-crystal analysis. The crystal belongs to triclinic system, space group P-1, crystal parameter: a=0.75333（4）nm,b=0.98398（5）nm,c=1.26177（7）nm,α=96.4060（10）°,β=94.6070（10）°,γ=102.8400（10）°,Z=2，R₁=0.0270,wR₂=0.0669. The tin（Ⅳ） ion is hexacoordinated in a octahedral geometry.（5） Schiff base complex Ni（OS）, where H₂OS is N,N’-bis（salicylidene）-o-phenylenediamine, was synthesized and characterized by IR spectrum, fluorescence spectrum and single-crystal analysis. The crystal belongs to rhombic system, space group P 2₁2₁ 2₁, crystal parameter: a=0.54649（8）nm,b=1.6588r2)nm,c=1.7281（2）nm,α=90°,β=90°,γ=90°,Z=4,R₁=0.0246,wR₂=0.0551.The nickel atom is in a planar coordination site of [N₂O₂], and it deviates from the mean plane by only 0.71 pm.（6） The complex [Cu（phen）₂Cl]·ClO₄·H₂O, where phen is 1,10-phenanthroline, was synthesized. Its crystal structure has been determined by X-ray analysis. The crystal belongs to monoclinic system, space group P2₁/n, a=1.18086（8）nm,b=1.52855（10）nm,c=1.29572（9）nm,α=90°,β=93.1770（10）°,γ=90°,V=2.3352（3）nm³,Z=4,R₁=0.0481,wR₂=0.1424. The copper atom is in a triangular bipyramid geometry.（7） The ternary complex [Cu（C₈H₄O₄,）(C₁₂H₈N₂)（H₂O）]·（CH₃）₂NCHO, where C₈H₄O₄^2- is 3-carboxylsalicylaldehyde dianion and C₁₂H₈N₂ is o-phenanthroline, was synthesized. The crystal belongs to triclinic crystal system, P-1 space group, with a=0.96936（6）nm,b=1.09020（12）nm,c=1.12800（7）nm,α=103.8340（10）°,β=109.7640（10）°,γ=98.6040（10）°,Z=2,R₁=0.0360,wR₂=0.1108. The Cu（Ⅱ） ion is pentacoordinated in a tetragonal pyramidal geometry, with two O atoms of 3-carboxylsalicylaldehyde dianion and two N atoms of o-phenanthroline occupying the square plane, and the water’s O atom locating at the axial site.更多还原