基于水杨醛类席夫碱构筑的Fe(Ⅲ)、Co(Ⅲ)、混价Mn(Ⅱ))/Mn(Ⅲ)配合物的合成、晶体结构及磁性
Syntheses, Crystal Structures and Magnetic Properties of Fe(Ⅲ), Co(Ⅲ) and Mixed Valence Mn(Ⅱ)/Mn(Ⅲ) Complexes Based on a Schiff Base Ligand Derived From Salicylaldehyde
作者单位E-mail
高喜凤 山东省食品药品检验研究院, 济南 250101  
刘敬松 齐鲁制药有限公司, 济南 250101  
杨培培 淮北师范大学化工系, 淮北 235000  
刘艳明 山东省食品药品检验研究院, 济南 250101 msymliu@163.com 
张喜琦 山东省食品药品检验研究院, 济南 250101  
祝建华 山东省食品药品检验研究院, 济南 250101 zhujianhua9@sina.com 
摘要: 以3-甲氧基水杨醛与乙醇胺缩合得到席夫碱化合物hmmpH2(hmmpH2=2-[(2-羟乙基亚氨基)甲基]-6-甲氧基苯酚),以hmmpH2为配体合成了配合物[Fe2(hmmp)2(hmmpH)2]·1.5CH3CN·0.5H2O(1)和[Co2Na(hmmp)2(N32(CH3O)(CH3OH)2](2)。以3,5-二溴水杨醛与乙醇胺缩合得到化合物hmdbrpH2(hmdbrpH2=2-[(2-羟乙基亚氨基)甲基]-4,6-二溴苯酚),以hmdbrpH2为配体合成了一个混价三核配合物[Mn(Ⅱ)Mn(Ⅲ)2(hmdbrp)2(O2CPh)4(CH3OH)2]·2CH3CN·2CH3OH(3)(HO2CPh为苯甲酸)。对配合物分别进行了元素分析、X射线单晶衍射分析,还对13进行了磁性研究。单晶结构分析表明配合物1中2个六配位的Fe(Ⅲ)离子通过2个醇羟基氧原子相连形成二聚体结构,配合物2中Co(Ⅲ)也为六配位,通过2个甲醇中氧原子相连形成双核结构,配合物3为一混价三核锰结构,3个Mn离子呈线性排列。磁性测试表明配合物1中Fe(Ⅲ)离子之间存在反铁磁相互作用,配合物3的三核锰单元内Mn(Ⅱ)、Mn(Ⅲ)离子之间存在反铁磁相互作用。
关键词: 席夫碱  混价  晶体结构  磁性
基金项目: 安徽省高校省级自然科学基金重点项目(No.KJ2015A066)资助。
Abstract: The Schiff base hmmpH2 (hmmpH2=2-[(2-hydroxyethylimino)methyl]-6-methoxyphenol) was synthesized by o-vanillin and ethanolamine. Complexes[Fe2(hmmp)2(hmmpH)2]·1.5CH3CN·0.5H2O (1) and[Co2Na((hmmp)2(N3)2(CH3O)(CH3OH)2] (2) were synthesized by using hmmpH2 ligand. The Schiff base hmdbrpH2 (hmdbrpH2=2-[(2-hydroxyethylimino)methyl]-4,6-dibromophenol) was synthesized by 3,5-dibromosalicylaldehyde and ethanolamine. Complex[Mn(Ⅱ)Mn(Ⅲ)2(hmdbrp)2(O2CPh)4(CH3OH)2]·2CH3CN·2CH3OH (3) was synthesized by using hmdbrpH2 ligand. These complexes were fully characterized by elemental analysis and X-ray single crystal diffraction, and complexes 1 and 3 were also studied by magnetic investigation. The structural analysis indicates that in complex 1 two six-coordinated Fe(Ⅲ) ions are bridged by two alcoholic hydroxyl atoms to form a dimer structure. In complex 2, Co(Ⅲ) is six-coordinated with an octahedral coordination environment and the two Co(Ⅲ) ions are bridged by two O atoms from CH3OH constructing a binuclear complex. The complex 3 is a mixed valence trinuclear structure, with three Mn ions in linear array. Magnetic study indicates that the antiferromagnetic interaction exist between Fe(Ⅲ) ions in complex 1, and in complex 3 antiferromagnetic interactions exist between the Mn(Ⅱ) and Mn(Ⅲ) ions in the trinuclear manganese unit.
Keywords: Schiff base  mixed valence  crystal structure  magnetic property
投稿时间:2016-12-12 最后修改时间:2017-02-27
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高喜凤,刘敬松,杨培培,刘艳明,张喜琦,祝建华.基于水杨醛类席夫碱构筑的Fe(Ⅲ)、Co(Ⅲ)、混价Mn(Ⅱ))/Mn(Ⅲ)配合物的合成、晶体结构及磁性[J].无机化学学报,2017,33(4):630-636.
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