【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.更多还原

【Abstract】 A novel chiral Salen 1 and its dinuclear Salen Mn complex 2(host) wer e synthesized and charactered by elemental analysis,1H NMR,FT-IR,UV-Vis,and CD spectra.The molecular recognition of 2 with imidazoles and pydines were studied by method of UV-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 膔Hm,膔Sm were also calculated.The result s 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 th e results of quantum chemical calculation .更多还原