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三脚架型稀土配合物的1H NMR研究

杨小平,匡代彬,郑康成,苏成勇,刘汉钦*   

  1. 中山大学化学与化工学院物化所,广州 510275
  • 收稿日期:2000-11-13 修回日期:2000-12-01 出版日期:2001-03-05 发布日期:2001-03-05
  • 作者简介:杨小平(1969-),男,博士生.*通讯联系人
  • 基金资助:
    国家自然科学基金,北京大学国家稀土重点实验室开放基金资助项目.

1H NMR STUDIES ON THE LANTHANIDE COMPLEXES OF TRIPODAL LIGAND

YANG Xiao-ping, KUANG Dai-bin, ZHENG Kang-cheng, SU Cheng-yong and LIU Han-qin*   

  1. Institute of Physical Chemistry, School of Chemistry and Chemical Engine ering, Zhongshan University, Guangzhou 510275
  • Received:2000-11-13 Revised:2000-12-01 Online:2001-03-05 Published:2001-03-05
  • About author:*Correspondence author
  • Supported by:
    国家自然科学基金,北京大学国家稀土重点实验室开放基金资助项目.

摘要:

报道了稀土离子与三脚架配体N,N-二(2-苯并咪唑亚甲基)-N-(2-吡啶亚甲基)胺(L)和安替吡啉(L′)形成的二元稀土及三元稀土固体配合物的制备. 配合物在不同溶液中的1H NMR,并结合配合物晶体结构、IR及电荷布居计算,探讨了配体在溶液中的配位形式.在CH\-3CN中,配体L以四齿配位,L′用羰基氧
配位,稀土离子在二元与三元配合物中的配位数分别为10和7.在三元配合物中,由于三个L′的空间位阻作用,将阴离子与溶剂分子排斥出稀土离子的配位层.在DMSO中,由于强极性的溶剂分子参与Ln3+的配位竞争,配合物发生了解离.

关键词:

Abstract:

The preparation of binary and ternary solid complexes of lanthanide ions with tripodal ligand N,N-bis(2-benzimidazolylmethyl)-N-(2-pyridylmethyl)amine
(L) and antipyrine (L′) is reported in this article. The coordination forms of the complexes in various solutions were studied by 1H NMR, supported by the si
ngle crystal x-ray diffraction and IR data, as well as the ab initio calculation. In CH3CN solution, L coordinates to the metal atoms with four nitrogen atoms, while L′ with its carbonyl oxygen only. The coordination numbers of the binary and ternary complexes were 10 and 7 respectively. In the ternary complexes,
anions and solvent molecules could not enter the coordination sphere due to the steric effect of three big L′molecules. The complexes dissociate in the strongly polar DMSO solution.

Key words: Lanthanide complex, Tripodal ligand, Antipyrine, 1H NMR, Coordinate form

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