高等学校化学学报 ›› 2014, Vol. 35 ›› Issue (1): 12.doi: 10.7503/cjcu20130671

• 研究论文: 无机化学 • 上一篇    下一篇

2-(羟甲基)-N-甲基咪唑桥联Mn2Mn2四核配合物的合成、 结构和磁性

石文博, 寇会忠()   

  1. 清华大学化学系, 北京 100084
  • 收稿日期:2013-07-17 出版日期:2014-01-10 发布日期:2013-12-13
  • 作者简介:联系人简介: 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:
    国家重点基础研究发展计划(批准号: 2013CB933403)和国家自然科学基金(批准号: 91222104, 21771103)资助

Synthesis, Crystal Structure and Magnetic Properties of Tetranuclear Mn2Mn2 Complexes Based on 2-(Hydroxymethyl)-N-methylimidazole

SHI Wenbo, KOU Huizhong*()   

  1. Department of Chemistry, Tsinghua University, Beijing 100084, China
  • Received:2013-07-17 Online:2014-01-10 Published:2013-12-13
  • Contact: KOU Huizhong E-mail:kouhz@mail.tsinghua.edu.cn
  • Supported by:
    † Supported by the National Key Basic Research Program of China(No.2013CB933403) and the National Natural Science Foundation of China(Nos.91222104, 21171103)

摘要:

报道了3个2-(羟甲基)-N-甲基咪唑(Hhmmi)桥联的Mn2Mn2四核配合物[Mn4(hmmi)6(DMF)2·(N3)2](ClO4)2(1), [Mn4(hmmi)6(H2O)2(N3)2](ClO4)2(2)和[Mn4(hmmi)6Cl4]·6CH3CN(3·6CH3CN)的合成、 晶体结构和磁性. 在配合物1 ~ 3中, 中心结构皆为四核蝶形混合价Mn结构, 2个Mn占据蝶形两翼位置, 2个Mn占据蝶形中间位置. Mn离子间通过hmmi-上的μ3-烷氧原子桥联, 相应Mn—O—Mn键角为101.3°~103.4°; 而Mn-Mn离子间通过hmmi-上的μ3-和μ2-烷氧原子桥联, 相应Mn—O—Mn键角为92.5°~113.7°. 对配合物1~3进行变温磁化率拟合, 结果表明, Mn-Mn间呈铁磁相互作用, 而Mn-Mn间以及Mn4分子间存在较弱的铁磁或反铁磁耦合.

关键词: 2-(羟甲基)-N-甲基咪唑, 锰, 四核配合物, 磁性, 混合价

Abstract:

Three new 2-(hydroxymethyl)-N-methylimidazole-bridged tetranuclear Mn2Mn2 complexes [Mn4(hmmi)6(DMF)2(N3)2](ClO4)2(1), [Mn4(hmmi)6(H2O)2(N3)2](ClO4)2(2) and [Mn4(hmmi)6Cl4]·6CH3CN(3·6CH3CN)[Hhmmi=2-(hydroxymethyl)-N-methylimidazole] were synthesized, and their crystal structures and magnetic properties were studied. In the mixed-valent [Mn4]2+ cores for complexes 1—3, Mn are located at the sides, and Mn in the middle. Best fit to the experimental data for complexes 1—3 suggests the presence of ferromagnetic coupling for Mn-Mn, while weak ferromagnetic or antiferromagnetic coupling for Mn-Mn or intermolecular interaction.

Key words: 2-(Hydroxymethyl)-N-methylimidazole, Manganese, Tetranuclear complex, Magnetism, Mixed-valent

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