化学学报 ›› 1991, Vol. 49 ›› Issue (4): 376-381. 上一篇    下一篇

研究论文

氯冉酸阴离子桥联双核铜(II)配合物的合成和磁性

郝松琪;姜宗慧;廖代正;张智勇;王耕霖   

  1. 南开大学元素有机化学重点实验室;南开大学化学系.天津(300071)
  • 发布日期:1991-04-15

Synthesis and magnetic properties of binuclear copper(II) complexes using the dianions of chloranilic acids as bridging ligands

Hao Songqi;Jiang Zonghui;Liao Daizheng;Zhang Zhiyong;Wang Genglin   

  1. Nankai Univ, Dept Chem.Tianjin(300071)
  • Published:1991-04-15

本文合成了五种以氯冉酸二价阴离子为桥联配体的Cu(II)单核([CuLCA].H~2O)和双核([Cu~2L~2CA](ClO~4)~2配合物:[Ca(phen)CA].H~2O(1),[Cu~2(phen)~2CA](ClO~4)~2(2),[Cu(NO~2-phen)CA].H~2O(3),[Cu~2(NO~2-phen)~2CA](ClO~4)~2(4)和[Cu~2(bpy)~2CA](ClO~4)~2(5)。经元素分析、红外、固体紫外、顺磁共振、磁化率及变温磁化率的测定对上述各配合物进行了表征。配合物1,3可能是通过水分子中的氢键将两个[CuLCA]单元联接而缔合的假双聚体。配合物2,4,5则由阳[Cu~2L~2CA]^2^+阳离子和弱配位的ClO~4^-阴离子所组成。双核配合物中Cu(II)离子的几何构型可能为畸变的四方锥。所有五种配合物均难溶于水及常见有机溶剂。上述配合物的室温ESR谱呈现ΔM~s=2的从单重态到三重态的半场跃迁。配合物2,5的变温磁化率(4-300K)已测得,利用Heisenberg模型确定交换参数J值为-29.2和-25.7cm^-^1。表明在此类桥联配合物中,两核间存在着反铁磁性交换耦合作用。

关键词: 磁性, 合成, 氯冉酸, 氯离子, 双核配合物, 单核配合物, 桥联配合物, 元素分析, 红外, 紫外

Five new copper(II) complexes containing bidentate terminal ligands and dianions of chloranilic acids (CA) have been synthesized, namely [Ca(phen)CA].H~2O(1; phen=o-phenanthroline), [Cu~2(phen)~2CA](ClO~4)~2 (2), [Cu(NO~2-phen)CA].H~2O(3; NO~2-phen=5-Nitro-o-phenanthroline), [Cu~2(NO~2-phen)~2CA](ClO~4)~2(4) and [Cu~2(bpy)~2CA](ClO~4)~2(5; bpy=2, 2'-biphridyl). CA acts as bridging ligand in these compounds. All complexes have been characterized by elemental analyses, IR, electronic spectra, ESR, susceptibility and variable-temperature magnetic susceptibility. Complex 1, 3 might be associated in pseudodimeric entities formed by two [CuLCA].H~2O moieties connected via hydrogen bonding whereas the structures of 2, 4 and 5 are built up by dimeric [Cu~2L~2CA]^2^+ cations and weak coordinated ClO~4^- anions. The copper(II) ion coordination geometry is probably distorted square pyramidal in the binuclear complexes. These complexes are very poorly soluble in water or common organic solvenos. Room-temperature ESR spectra of all the complexes studied show that ΔM~s=2 half-field transitions (Singlet-to-triplet). The variable- temperature magnetic susceptibilities of 2 and 5 have been measured (4- 300K). Based on the Heisenbery model, the exchange parameter, J, was found to be -29.2 and -25.7cm^-^1 for 2 and 5, respectively. An antiferromagnetic exchange interaction was suggested between the metal ions in these complexes.

Key words: MAGNETISM, SYNTHESIS, CHLORINE ION, DINUCLEAR COMPLEX, MONONUCLEAR COMPLEX, ELEMENTAL ANALYSIS, INFRA- RED, UV-DETECTOR, PARAMAGNETIC RESONANCE, TRIPLET

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