高等学校化学学报

高等学校化学学报 ›› 1998, Vol. 19 ›› Issue (3): 331.

• 论文 •    下一篇

双臂套索冠醚双核铜(Ⅱ)配合物的磁性质研究

张华1, 王国雄2, 季峰2, 王谷丰2, 王德枌2, 胡宏纹2, 姚天扬2   

  1. 1. 北京大学化学与分子工程学院, 智能材料研究中心, 北京, 100871;
    2. 南京大学化学系, 南京, 210093
  • 收稿日期:1997-03-05 出版日期:1998-03-24 发布日期:1998-03-24
  • 通讯作者: 王国雄
  • 作者简介:张华,男,25岁,博士研究生.

Studies on the Magnetic Properties of Binuclear Copper(Ⅱ) Complex of a Bibracchial Lariat Ether

ZHANG Hua1, WANG Guo-xiong2, JI Feng2, WANG Gu-Feng2, WANG De-Fen2, HU Hong-Wen2, YAO Tian-Yang2   

  1. 1. Center for Intelligent Materials Research, College of Chemistry and Molecular Engineering, Peking University, Beijing, 100871;
    2. Department of Chemistry, Nanjing University, Nanjing, 210093
  • Received:1997-03-05 Online:1998-03-24 Published:1998-03-24

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摘要： 测定了双臂套索冠醚双核铜(Ⅰ)配合物[Cu2L(OH)](ClO4)3Me2CO(L=N,N'-二(8-喹啉甲基)-1,4,10,13-四氧-7,16-二氮环八环)的变温磁化率(4～300K),所加场强为5.O×105A/m.拟合了变温磁化率数据,得到J=-279.cm-1;加上分子场校正后,得J=-257.7cm-1,Zj'=-30.1cm-1.拟合结果表明,分子间存在反铁磁性交换作用,而分子内的磁交换(J＜500cm-1)还未大到使其反铁磁性交换作用变为抗磁性.用自旋倾斜体系解释了其反常的χm-H图.晶体结构和Cu2+3d轨道的分析表明,磁交换作用是通过OH桥进行的.比较了另外2个类似的双核铜(Ⅰ)大环OH桥联配合物,得出了J值和轨道重叠之间的关系.

关键词: 双核铜(Ⅰ)配合物, 双臂套索冠醚, 磁性

Abstract: The variable temperature(4～300 K) magnetic susceptibility of binuclear copper(Ⅱ) complex of the bibracchial lariat ether [Cu2L(OH) (ClO4)3Me2CO(L= N,N'-bis(8-quinolylmethyl)-1,4,10,13-tetraoxa-7,16-diazacyclooctadecane) (1) was measured in an appropriate magnetic field of 500000 A/m. The strongly antiferromagnetic interaction constants are as follows: J =-257.7 cm-1, Zj'=-30.1 cm-1. It is shown that there is an antiferromagnetic interaction between molecules. The | J | value (<500 cm-1 ) is not large enough to lead to the diamagnetic coupling. The plot of χm-H, which is different from the normal plot of χm-H, is explained through the spin canting phenomenon. By analyzing the crystal structure of the complex and 3d orbitals of two Cu2+ cations, we suggest that the exchange path is through OH bridge. Compared with the other two analogous binuclear copper(Ⅱ) complexes coordinated by macrocycle ligand and bridged by OH, we analyzed the correlation between J value and the overlap of orbitals.

Key words: Binuclear copper(Ⅱ) complex, Bibracchial lariat ether, Magnetic properties

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