新型氮杂大环化合物的研究Ⅲ.取代不对称多齿氮杂大环化合物的合成、表征与配位性能

Studies on New Aza-Macrocycles Ⅲ. Syntheses, Characterization and Complexing Behavior of Substituted Unsymmetrical Aza-Macrocycles

合成了四种以Nsp2 和Nsp3为配位原子的取代不对称多齿氮杂大环化合物 ,制备了它们与不同金属离子的配合物 ,通过元素分析和光谱表征 ,研究了配体的结构与其配位性能的关系 .以吡啶环为侧链功能基的配体L1和L2可根据其环大小选择性地识别Na+或K+离子 ,与过渡金属离子形成 1∶1型配合物 ,而与Hg2 +,Cd2 +等离子则形成1∶2型配合物 .大环配体L3与Co2 +和Na+离子形成的双核配合物中两个冠醚环和一个Na+离子形成夹心配位结构 .L5环中有两个配位中心 ,因而可同时与两个Ru2 +离子配位 .L1和L2

Five new unsymmetrical aza-macrocycles, incorporating sp 2 and sp 3 nitrogen atoms as donor sites and with donor group-bearing side arms attached to the sp 3 nitrogen atoms, L 1-L 5, were synthesized. Their complexes with different kinds of metal cations such as Na +, K +, Cu 2+, Co 2+, Ni 2+, Hg 2+, Cd 2+, Ru 2+, were prepared and characterized by EA, IR, UV, NMR and MS spectroscopy. Some of the ligands can efficiently transport alkali and transition metal cations across an organic membrane with high transport selectivity ratio, especially in the case of Na +/K + selectivity for L 1 and Hg 2+/Ni 2+ selectivity for L 2.