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化学学报
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化学学报 ›› 2005, Vol. 63 ›› Issue (10): 919-923. 上一篇    下一篇

研究论文

混合价四核锰配合物[Mn4O2(ClCH2COO)7(bipy)2]•H2O的合成、晶体结构及性质研究

任颜卫，李王君*，吴爱芝，李淑妮，张逢星   

  1. (西北大学化学系 陕西省物理无机化学重点实验室 西安 710069)
  • 投稿日期:2004-09-27 修回日期:2005-01-24 发布日期:2010-12-10
  • 通讯作者: 李王君

Synthesis, Structure and Properties of Mixed-Valence Tetranuclear Manganese Complex [Mn4O2(ClCH2COO)7(bipy)2]•H2O

REN Yan-Wei, LI Jun*, WU Ai-Zhi, LI Shu-Ni, ZHANG Feng-Xing   

  1. (Department of Chemistry, Northwest University, Shaanxi Key Laboratory of Physico-inorganic Chemistry, Xi′an 710069)
  • Received:2004-09-27 Revised:2005-01-24 Published:2010-12-10
  • Contact: LI Jun

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在乙腈溶液中, 由混合价三核锰配合物[Mn3O(ClCH2COO)6(py)2]•(H2O) (py为吡啶)与2,2′-联吡啶(bipy)反应合成了混合价(Mn3IIIMnII)四核锰配合物[Mn4O2(ClCH2COO)7(bipy)2]•H2O. 采用元素分析、红外光谱、热分析和X射线单晶衍射法确定了其组成和结构. 标题化合物晶体属于三斜晶系, 空间群P-1, 晶胞参数: a＝0.89854(13) nm, b＝1.4027(2) nm, c＝1.9037(3) nm, α＝93.518(3)°, β＝96.736(3)°, γ＝94.875(3)°, V＝2.3680(6) nm3, Z＝2, Dc＝1.734 g/cm3, F(000)＝1238, GOF＝1.036, R1＝0.0592, wR2＝0.1162 [I＞2σ(I)]. 在标题化合物中, 配位结构单元中心为一蝶型[Mn4(μ3-O)2]7＋多核簇, 含有2个Mn3(μ3-O)单元, 具有近似C2对称轴. 4个Mn离子均为六配位, 外围配体为7个氯乙酸根和2个2,2′-联吡啶, 处于变形的八面体环境. 变温磁化率研究表明标题化合物在整体上表现为反铁磁性耦合作用, 但在低温下的磁相互作用较为复杂.

关键词: 混合价化合物, 氧桥四核锰配合物, 晶体结构, 磁性质, 热分解

The reaction of trinuclear manganese complex [Mn3O(ClCH2COO)6(py)2]•(H2O) with 2,2′-bipyridine in CH3CN led to the new mixed valence tetranuclear Mn3IIIMnII complex of formulation [Mn4O2(ClCH2COO)7(bipy)2]•H2O. The structure and chemical composition of title complex were determined by elemental analysis, IR spectrum, thermal analysis and X-ray diffraction analysis. The crystal structure belongs to triclinic system with space group P-1 and a＝0.89854(13) nm, b＝1.4027(2) nm, c＝1.9037(3) nm, α＝93.518(3)°, β＝96.736(3)°, γ＝94.875(3)°, V＝2.3680(6) nm3, Z＝2, Dc＝1.734 g/cm3, F(000)＝1238, GOF＝1.036, R1＝0.0592, wR2＝0.1162 [I＞2σ(I)]. The analysis of the crystal structure indicates that the title complex has a butterfly [Mn4(μ3-O)2]7＋core, which consists of two Mn3(μ3-O) units, with approximate C2 symmetric axis. The four manganese atoms are all six-coordinated with seven chloroacetate acid anions and two 2,2′-bipyridine molecules, forming distorted octahedron configuration. Variable temperature magnetic susceptibility of the title complex showed the existence of intramolecular antiferromagnetic interaction, and it was intricate at relatively low temperature.

Key words: mixed-valence complex, tetranuclear manganese complex, crystal structure, magnetic property, thermal decomposition