过渡金属Schiff碱配合物的合成、晶体结构及性质研究

发布时间：2018-04-15 22:39

  本文选题：Schiff碱 + 过渡金属配合物　； 参考：《兰州交通大学》2016年硕士论文

【摘要】：过渡金属Schiff碱类配合物因其结构的复杂多样、独特和新颖的性能,得到了大多科学家们的注意。这类化合物通常是由含有氨基(-NH_2)的化合物与醛或酮发生缩合反应而得到的含有C=N基团的化合物,其C=N上的N原子能够提供一对孤对电子给大部分过渡金属离子从而得到金属配合物,而使其在化学分析、生物医药、农药、催化、超分子、分子磁性及材料科学等诸多领域具有着广泛的用途。在本论文中,首先合成了4-氨基苯乙酮O-苄基肟;然后通过它与2-羟基萘甲醛和3,5二氯水杨醛缩合反应,合成了2种不同的氨基苯乙酮肟类化合物,它们分别为:1-(4-{[(2-羟萘基)次甲基]氨基}苯基)乙酮O-苄基羟氨肟配体(HL~1)、1-(4-{[(3,5-二氯-2-羟苯基)次甲基]氨基}苯基)乙酮O-苄基羟氨肟配体(HL~2);用2-氨基-3-羟基吡啶分别与合成的3-醛基-4-羟基香豆素和3,5二溴水杨醛反应,合成了2种不同的2-氨基-3-羟基吡啶类化合物,它们分别为:4-羟基-3-[(3-羟基-吡啶-2-亚氨基)]-苯并吡喃-2-酮配体(HL3)、2-[(3,5-二溴-2-羟基)-氨基]-吡啶-3-醇配体(HL~4)。通过自然放置挥发溶剂的方法,使得5个配合物单晶被培养出来,配合物单晶分别:[Cu(L~1)_2](1),[Ni(L~1)_2](2),[Mn4(L~2’)_2(μ3-OMe)_2(μ2-OMe)_2(Me OH)_2](3),[Ni2(L3)_2(D MF)_2](4),[Zn2(L~4)_2(H_2O)_2]·2DMF(5),对这4种配合物进行了红外、紫外、荧光等性质表征,并且利用X-射线单晶结构衍射法确定了它们的化学组成及空间结构。其相关的晶体学数据为:配合物1:化学组成为C_(52)H_(42)CuN_4O_4,Mr=850.44,属于Monoclinic,空间群I2/c,晶胞参数:a=21.8573(13)?,b=5.8605(4)?,c=33.683(2)?,α=90.00°,β=97.428(5)°,γ=90.00°,Z=4,V=4278.4(5)?~3,R_1=0.0554,wR_2=0.1042;配合物2:化学组成为C_(52)H_(42)NiN_4O_4,Mr=845.60,属于Triclinic,空间群P1,晶胞参数:a=5.6602(6)?,b=10.585(2)?,c=18.053(3)?,α=76.312(17)°,β=89.215(11)°,γ=78.818(13)°,Z=1,V=1030.3(3)?~3,R_1=0.0866,wR_2=0.1353;配合物3:化学组成为C_(40)H_(40)Cl_8Mn_4O_(16),Mr=1280.08,属于Triclinic,空间群P1,晶胞参数:a=9.3045(13)?,b=11.792(3)?,c=12.408(3)?,α=70.12(2)°,β=75.412(16)°,γ=80.928(15)°,Z=1,V=1235.1(5)?~3,R_1=0.0823,wR_2=0.1922;配合物4:化学组成为C_(18)H_(15)N_3NiO_5,Mr=412.04,属于Monoclinic,空间群P21/c,晶胞参数:a=9.9121(4)?,b=14.1192(6)?,c=12.4016(5)?,α=90°,β=102.395(5)°,γ=90°,Z=4,V=1695.16(13)?~3,R_1=0.0361,wR_2=0.0815;配合物5:化学组成为C_(12)H_8Br_2N_2O_3Zn·C_3H_7NO,Mr=526.49,属于Monoclinic,空间群P21/c,晶胞参数:a=11.5966(6)?,b=13.9483(4)?,c=11.3506(6)?,α=90°,β=105.547(5)°,γ=90°,Z=4,V=1768.82(14)?~3,R_1=0.0533,wR_2=0.1330.
[Abstract]:Transition metal Schiff base complexes have attracted the attention of most scientists because of their complex and diverse structures, unique and novel properties.These compounds are usually compounds containing Con N groups, which are obtained by condensation of compounds containing amino acids and aldehydes or ketones.The N atom on its Con N can provide a pair of lone pairs of electrons to most transition metal ions to get metal complexes, which can be used in chemical analysis, biomedicine, pesticides, catalysis, supramolecular chemistry,Molecular magnetism and material science are widely used in many fields.In this thesis, 4-aminoacetophenone O-benzyl oxime was synthesized firstly, and then two kinds of aminoacetophenone oxime compounds were synthesized by condensation of 2-hydroxynaphthalene formaldehyde and 3o 5-dichloro-salicylic aldehyde.They are: 1-1-[[[2-hydroxynaphthyl) methylene] amino} phenyl] acetone] -benzylamine oxime ligand HL-1HYDROXYLHYDROXYL 4- {[CHLORON-2-HYDROXYLPHENYL] aminophenyl} phenyl) ethanone O- benzyl hydroxaminoxime ligand HL2; 2-amino-3-hydroxypyridine, respectively.Reaction with 3-Aldol -4-hydroxycoumarin and 3- (5-dibromo-salicylidene),Two kinds of 2-amino-3-hydroxypyridine compounds were synthesized. They are: 1 -4-hydroxy-3- [3-hydroxy-pyridine-2-imino] -benzopyran -2-one ligand HL-2- [tribromo-5-dibromo-2-hydroxypyridyl] -pyridin-3-ol ligand HL-4.閫氳繃鑷�鐒舵斁缃�鎸ュ彂婧跺墏鐨勬柟娉，

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