物理化学学报 >> 2003, Vol. 19 >> Issue (04): 320-325.doi: 10.3866/PKU.WHXB20030408

研究论文 上一篇    下一篇

手性双核Salen配合物的谱学性质

胡国航;阮文娟;张玉玲;韩华;朱志昂   

  1. 南开大学化学系,天津　300071
  • 收稿日期:2002-07-15 修回日期:2002-10-28 发布日期:2003-04-15
  • 通讯作者: 阮文娟 E-mail:wjruan@nankai.edu.cn

Study on Spectra Properties of Chiral Dinuclear Salen Complex

Hu Guo-Hang;Ruan Wen-Juan;Zhang Yu-Ling;Han Hua;Zhu Zhi-Ang   

  1. Department of chemistry, Nankai University, Tianjin　300071
  • Received:2002-07-15 Revised:2002-10-28 Published:2003-04-15
  • Contact: Ruan Wen-Juan E-mail:wjruan@nankai.edu.cn

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摘要： 合成了四个新型的手性双核(R,R)Salen配合物[(Cu)2L•H2O(2), (Ni)2L(3), (Zn)2L•H2O(4), (MnCl)2L•2H2O(5)], (其中L是由(R,R)环己二胺、 3,5-叔丁基水杨醛、 5,5’-亚甲基二水杨醛为原料合成的手性二聚Salen配体(1)).用元素分析、NMR、FT-IR、UV-Vis、CD光谱对配体和配合物进行了表征.在与单核的Salen配体和配合物比较的基础上，详细讨论了红外光谱、电子吸收光谱、圆二色光谱性质.发现双核配体和配合物的电子吸收光谱吸收峰的位置和形状与单核的配体和配合物基本一致，而吸收峰的强度有近似两倍的关系.另外， 用激子偶合理论解释了此类手性化合物圆二色谱的Cotton效应和Cotton分裂. Cotton分裂的方向依赖于环己二胺的构象.(R,R)环己二胺决定了Salen化合物的手征性为负， Cotton分裂的正负两部分分别处于高能区和低能区.

关键词: 手性Salen(N,N’-bis-(salicylaldehyde)ethylenediimine的缩写)配体, 双核Salen配合物, 谱学性质

Abstract: Four novel chiral dinuclear Salen complexes [(Cu)2L•H2O(2), (Ni)2L(3), (Zn)2L•H2O(4), (MnCl)2L•2H2O(5)] have been synthesized (L is chiral dimeric Salen ligand which is synthesized from (R, R)-diaminocyclohexane, 3,5-di-tert-butyl salicylaldehyde, 5,5′-methylene-di-salicylaldehyde). These ligands and complexes were characterized by elemental analysis, 1H NMR, UV-Vis, FT-IR, CD spectra. The UV-Vis spectra were compared with those of monomeric Salen ligand and complex. It was found that the position and shape of absorption band are similar to those of the corresponding monomeric compounds, but the values of the absorption peak(ε) are approximately two folds larger. Furthermore Cotton effect and Cotton split of CD spectra of these chiral compounds were explained by the exciton interaction theory. It seemed that the direction of Cotton split depend on the configuration of diaminocyclohexane. (R, R)-diaminocyclohexane termined the chirality of Salen compounds as negative, and the positive and negative component of Cotton split lie at higher and lower energy respectively.

Key words: Chiral Salen(N,N′-bis-(salicylaldehyde) ethylenediimine)] ligands, 　Dinuclear Salen complexes, Spectra properties