新型手性双核Salen Mn的分子识别研究  

Molecular Recognition Property of Novel Dinuclear Chiral Salen Mn Complex

作　　者：袁瑞娟[1] 阮文娟[1] 朱必学[1] 曹小辉[1] 朱志昂[1] 

机构地区：[1]南开大学化学系,天津300071

出　　处：《物理化学学报》2005年第2期139-145,共7页Acta Physico-Chimica Sinica

基　　金：国家自然科学基金(20171024;20271030); 天津市自然科学基金(023604011); 国家教育部留学回国人员科研启动基金资助项目~~

摘　　要：合成了新型手性双Salen配体1及双核锰配合物2,并进行了表征.用紫外-可见光谱滴定法研究了主体双核SalenMn(2)与咪唑、吡啶类客体的分子识别行为.结果表明:对咪唑类客体的缔合常数顺序为K(Im)>K(2-MeIm)>K(N-MeIm);对吡啶类客体缔合常数顺序为K(4-MePy)>K(3-MePy)>K(Py).主体与所有客体的配位数均为2.测定了识别过程的热力学函数ΔrHm,ΔrSm,发现反应为放热、熵减过程.利用圆二色光谱研究了识别过程的Cotton效应.用分子力学方法研究了主客体的最低能量构象,结合量化计算结果对实验事实做了进一步解释.A novel chiral Salen 1 and its dinuclear Salen Mn complex 2 (host) were synthesized and charactered by elemental analysis, H-1 NMR, FT-IR, UV-Vis, and CD spectra. The molecular recognition of 2 with imidazoles and pydines were studied by method of U-V-Vis spectrophotometric titration, and it seems that the binding constants are in the orders of K(Im) > K(2-MeIm) > K(N-MeIm) (imidazoles), K(4-MePy) > K(3-MePy) > K(Py) (pydines). All of them have a coordination number of two. The thermodynamic functions Delta(r)H(m)(circle minus), Delta(r)S(m)(circle minus) were also calculated. The results indicated that the processes were exothermic and entropy decreasing. CD spectra of recognition process were studied and the results were consistent with those of thermodynamics. Moreover, the lowest energy configurations of host-guest were obtained by simulated annealing, and quantum chemical calculation was performed based on these configurations. The experimental phenomena was confirmed by the the results of quantum chemical calculation.

关 键 词：手性双核Salen MN配合物 分子识别 圆二色光谱 量化计算 

分 类 号：O643.3[理学—物理化学]