高等学校化学学报

高等学校化学学报 ›› 2012, Vol. 33 ›› Issue (05): 892.doi: 10.3969/j.issn.0251-0790.2012.05.005

• 研究论文: 无机化学 • 上一篇    下一篇

草酸-草酰胺混合桥联Mn(Ⅱ)-Cu(Ⅱ) 一维配合物的合成、晶体结构与磁性

胡孔球, 寇会忠   

  1. 清华大学化学系, 北京 100084
  • 收稿日期:2011-08-29 出版日期:2012-05-10 发布日期:2012-05-10
  • 作者简介:寇会忠, 男, 博士, 教授, 主要从事配位化学研究. E-mail: kouhz@mail.tsinghua.edu.cn
  • 基金资助:

    国家自然科学基金(批准号: 50873053)和国家自然科学基金委员会创新研究群体科学基金(批准号: 20921001)资助.

Synthesis, Crystal Structure and Magnetic Properties of an Oxalato- and Oxamido-bridged One-dimensional Mn(Ⅱ)-Cu(Ⅱ) Complex

HU Kong-Qiu, KOU Hui-Zhong   

  1. Department of Chemistry, Tsinghua University, Beijing 100084, China
  • Received:2011-08-29 Online:2012-05-10 Published:2012-05-10

PDF (PC)

被引次数

4

摘要： 合成了1个草酸-草酰胺混合桥联的双异金属配合物[Cu(L)(H2O)Mn(C2O4)]·4H2O(H2L为1,4,8,11-四氮杂环十四烷-2,3-二酮). 配合物由[Cu(Ⅱ)L(H2O)], Mn(Ⅱ), 草酸根和晶格水分子构成. Mn(Ⅱ)通过草酸根的交替桥联作用形成弯折的中性一维链状骨架[Mn(C2O4)]n, 而Mn(Ⅱ)剩余的2个配位点则由[CuL]上的2个草酰胺氧原子占据, 形成了草酸-草酰胺混合桥联一维双金属配合物. 而Cu(Ⅱ)为五配位, 轴向上由1个水分子占据. 磁性研究表明, 配合物中Cu(Ⅱ)-Mn(Ⅱ)间通过草酰胺传递反铁磁相互作用, 而Mn(Ⅱ)-Mn(Ⅱ)间亦通过草酸根离子存在反铁磁耦合. 通过MAGPACK软件对变温磁化率进行拟合, 得到JCu-Mn=-13.1 cm-1, JMn-Mn=-0.87 cm-1, g=2.01.

关键词: 草酸, 草酰胺, 锰, 铜, 磁性

Abstract: A new complex, [Cu(L)(H2O)Mn(C2O4)]·4H2O(H2L=1,4,8,11-tetraazacyclotetradecane-2,3-dione), was synthesized and structurally characterized by X-ray diffraction. The complex crystallizes in monoclinic space group P21/n with a=0.97471(5) nm, b=0.89316(5) nm, c=2.35635(11) nm, β=92.441(2)°, V=2.04951(18) nm3, Dc=1.691 Mg/m3, Z=4, R1=0.0607, wR2=0.1915(based on F2). The complex consists of [CuL(H2O)], Mn(Ⅱ), oxalate and lattice H2O molecules. Through the alternate oxalate bridges, the Mn(Ⅱ) ions form a zig-zag one-dimensional chain, while the other two coordination sites of the Mn(Ⅱ) ion are occupied by two oxygen atoms from L2- of [CuL(H2O)], giving rise to a mixed oxalate- and oxamido-bridged one-dimensional bimetallic complex. Magnetic studies show the presence of antiferromagnetic interaction between the Cu(Ⅱ) and Mn(Ⅱ) ions and between the adjacent Mn(Ⅱ) ions. Best fit to the experimental data by means of MAGPACK software gives the magnetic coupling constant of JCu-Mn=-13.1 cm-1 and JMn-Mn=-0.87 cm-1.

Key words: Oxalate, Oxamidato, Manganese, Copper, Magnetism

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