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手性Salen Zn配合物的合成及对咪唑类、吡啶类客体的分子识别研究 预览 被引量:21

Synthesis and Molecular Recognition of Chiral Salon Zn with Imidazoles and Pyridines
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摘要 合成并表征了手性Salen配体1及其Zn配合物2.详细讨论了配体及配合物的电子光谱和圆二色光谱性质.用紫外-可见光谱滴定法测定了主体2与4种咪唑、5种吡啶客体轴向配位反应的平衡常数,研究了主体分子2的分子识别行为.实验结果表明:各种客体的缔合常数,咪唑类按K(Im)>K(2-MeIm)>K(SMIm)>K(EMIm)顺序递减;吡啶类按K(Py)>K(3-Py)>K(3,5-Py)>K(2,4-Py)>K(2,4,6-Py)顺序递减.测定了识别过程的ΔrG m,ΔrH m,ΔrS m,发现该反应是放热、熵减小的过程.采用分子力学的方法考察了主客体的最低能量构象,并对该构象进行量子化学计算,从理论上对实验事实给予较好的解释. Chiral salen 1 and chiral salen Zn complex 2 were synthesized and characterized. The electronic spectra and circular dichroism spectra properties were discussed. By method of UV-vis spectrophotometer technique, the equilibrium constants of axial coordination reaction were measured between complex 2 and series of imidazoles or pyridines. The molecular recognition of the host 2 was studied. The results show that the equilibrium constants decrease in the orders of K(Im)>K(2-MeIm)>K(SMIm)>K(EMIm) (imidazoles) and K(Py)>K(3-Py)> K(3,5-Py)>K(2,4-Py)>K(2,4,6-Py) (pyridines). The thermodynamic parameters Δ rG  m, Δ rH  m and Δ rS  m of the recognition process were determined. It is found that the reaction is an exothermic process with entropy decreasing. In addition, the conformations with minimal energy of each host-guest molecular system were sought by molecular dynamics method. Quantum chemical calculations were performed on these conformations to explain the experimental data. A model of the recognition mechanism was constructed.
作者 张玉玲 阮文娟 李瑛 南晶 朱志昂 ZHANG, Yu-Ling RUAN, Wen-Juan LI, Ying NAN, Jing ZHU, Zhi-Ang (Department of Chemistry, Nankai University, Tianjin 300071, China)
机构地区 南开大学化学系
出处 《化学学报》 SCIE CAS CSCD 北大核心 2003年第2期 186-191,共6页 Acta Chimica Sinica
基金 国家自然科学基金,教育部留学回国人员科研启动基金
关键词 手性Salen配合物 合成 咪唑 吡啶 分子识别 量子化学计算 salen Zn, imidazole, pyridine, molecular recognition, quantum chemical calculation
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