中文摘要：

合成了系列溴代烷烃修饰的尾式锌卟啉，以此为主体，研究了尾式卟啉对含氮类客体吡啶、DABCO和吡嗪的轴向配位反应，测定了这些轴配反应的缔合常数．结果表明：四个主体对同一客体的平衡常数顺序为K^θ（ZnTPP）〉K^θ（ZnPC2Br）〉K^θ（ZnPC4Br）〉K^θ（ZnPC6Br）；而三个含氮类客体对于同一主体平衡常数顺序为K^θ（pyridine）〉K^θ（DABCO）〉K^θ（pyrazine）．主体与所有客体的配位数均为1．不同主体体系缔合常数的顺序与主客体结构均有关，是电子效应和空间效应的综合结果．研究了温度对缔合常数的影响，发现各类配位反应的平衡常数均随温度的升高而降低．根据不同温度下的K^θ，确定了配位过程的热力学函数△rHm^θ，△rSm^θ，发现反应均为放热、熵减过程．

英文摘要：

Association constants between ZnTPP, ZnPC2Br, ZnPC4Br, ZnPC6Br and pyridine, DABCO, pyrazine were determined in chloroform by means of UV-vis titration method. Association constants of the same guest and different hosts decreased in sequence KS（ZnTPP） 〉 K^θ （ZnPC2Br） 〉 K^θ （ZnPC4Br） 〉 K^θ（ZnPC6Br） ; while the association constants of the same host and different guests decreased in sequence K^θ （pyridine） 〉K^θ （DABCO） 〉K^θ（pyrazine）, and the coordination number is 1. This order gave the prove that electron effect was the majorer factor than space effect. The changes of standard molar enthalpy △rHm^θ and standard molar entropy △rSm^θ were obtained from the plots of lnK^θ vs. 1/T. It was found that the reaction is exothermic and the △rSm^θ is reductive.