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利用5-溴-3-甲氧基水杨醛和1,3-丙二胺、3-甲氧基水杨醛和乙二胺通过缩合反应得到2种希夫碱配体；借助叠氮酸根作为辅助配体，在缓慢挥发的条件下，与一水合乙酸铜、四水合氯化锰进行反应，制备得到了2种新的叠氮基桥联的磁性配合物[Cu2(BrLxtn)2(μ1,1-N3)2](1)(BrLxtn=(E)-2-(((3-aminopropyl)imino)methyl)-4-bromo-6-methoxyphenol)和[Mn_2Cu2(MeOen)2(μ1,1-N3)4](2)(MeOen=6,6'-((1E,1'E)-(ethane-1,2-diylbis(azaneylylidene))bis(methaneylylidene))bis(2-methoxyphenol))。利用元素分析、傅里叶红外光谱、X射线单晶衍射等方法对配合物1和2的结构进行了表征，结果表明：配合物1中，铜离子的配位几何构型为五配位变形四面体，三齿N_2O席夫碱和2个叠氮基配体与铜离子发生配位，形成含有叠氮基桥联的中心对称二聚体双核结构；配合物2中，铜离子与来自希夫碱配体的N_2O2单元配位，形成平面方形几何构型，而锰离子则与N_3O2单元配位，形成扭曲的三角双锥几何构型；2个CuMn希夫碱单元通过叠氮基相互桥接，形成了Mn_2Cu2四核结构。对配合物1和2的变温磁化率测试结果表明，在配合物1和2中，叠氮酸根桥联的金属离子间分别呈现反铁磁和铁磁耦合相互作用。
Abstract：Two Schiff base ligands were prepared by the condensation reactions of 5-bromo-3-methoxysalicylaldehyde with 1,3-propanediamine or 3-methoxysalicylaldehyde with ethylenediamine. These ligands were subsequently used to react with copper acetate monohydrate and manganese chloride tetrahydrate, using sodium azide as an auxiliary ligand under the slow volatilization conditions. This process resulted in the formation of two new azido-bridged magnetic complexes: [Cu2(BrLxtn)2(μ1,1-N3)2](1)(BrLxtn =(E)-2-(((3-aminopropyl)imino)methyl)-4-bromo-6-methoxyphenol) and [Mn_2Cu2(MeOen)2(μ1,1-N3)4](2)(MeOen = 6,6'-((1E,1'E)-(ethane-1,2-diylbis(azaneylylidene))bis(methaneylylidene))bis(2-methoxyphenol)). The structures of the obtained complexes 1 and 2 were characterized by elemental analysis, Fourier transform infrared spectroscopy and X-ray single crystal diffraction. The result showed that the complex 1 features an azide bridged dimeric binuclear copper(Ⅱ) structure. The coordination geometry of copper ions is a deformed five-coordinate tetrahedron formed by the tridentate N_2O Schiff base and two azide ligands. In complex 2, the copper ion is coordinated by N_2O2 unit from the Schiff base ligand to form a planar square geometry, while the manganese ion is coordinated with the N_3O2 unit to form a distorted triangular bipyramidal geometry. The two Cu-Mn-Schiff base units were bridged by azide groups, forming a Mn_2Cu2 tetranuclear structure. Investigation into the temperature-dependent magnetic susceptibilities of the complexes 1 and 2 indicated antiferromagnetic and ferromagnetic coupling interactions between the azide-bridged Cu or Mn ions, respectively.
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基本信息:
DOI：10.13367/j.cnki.sdgc.2026.04.008
中图分类号:O641.4
引用信息:
[1]王春彦,辛钰,张道鹏.叠氮基桥联Cu Ⅱ/Mn Ⅱ配合物的合成、结构和磁性研究[J].山东理工大学学报(自然科学版),2026,40(04):64-70+78.DOI:10.13367/j.cnki.sdgc.2026.04.008.
基金信息:
国家自然科学基金项目(22171166)
2026-04-16
2026-04-16