Studies On The Syntheses, Properties Of Ferrocene-functionalized Polyamines And Pendant-arm Tetra-aza Macrocycles

In this thesis, two new ferrocene-functionalized polyamines and three new pendant-armed pyridine-containing macrocyclic compounds were synthesized. The crystals of the two ferrocene-functionalized polyamines and four complexes of pendant-armed macrocycle with transition metal ions were obtained, their structures and conformations were characterized. The coordinative properties of the two ligands towards Ni2+,Cu2+,Zn2+,Cd2+,Pb2+ have been investigated by a combination of cycle voltammetry and 1H NMR spectroscopy. And the coordinative properties of two macrocyclic compounds towards Ni2+,Cd2+,Pb2+were studied. The main results obtained were as follows.1. The following two new ferrocene derivatives LI and L2 were designed and synthesized, and characterized by elemental analysis, IR, and NMR. Electrochem -ical investigations have demonstrated that the binding of Ni2+,Cu2+,Zn2+,Cd2+, Pb2+guest cations by LI and L2 results in shifts of the respective ferrocene-ferro -cenium redox couple to more positive potential. In addition, it can be concluded that LI forms mono-nuclear complexes with Cd2+, Ni2+ and binuclear complexes with Cu2+, Zn2+, Pb2+, and that L2 forms mono-nuclear complexes Ni2+, Zn2+, Cd2+, Pb2+ except Cu2+ which forms 1:2(ligand:cation) complexes with L2. Electro -chemical recognition competition experiments suggest both LI and L2 exhibit a degree of selectivity for the Cu2+ cation.2. Three novel pendant-armed pyridine-containing macrocyclic ligands L3, L4 and L5 were synthesized, characterized by elemental analysis, IR and NMR.The coordinative properties of three macrocyclic compounds towards transition metal ions were studied. And the crystal structures of complex of L3 with Cd2+, complexes of L4 with Ni2+, Cd2+and Pb2+ were determined. The X-ray structures of four complexes were as follows:(l)Cd2+coordinated with four nitrogen atoms of parent ligand L3, two oxygen atoms of NO3- ion and one oxygen atoms of the other NOs" ion, to form seven coordination center of deformed triangular prism;Cd (L3) ](N03)2 [Pb (L4) ](NO3)2(2)Pb2+coordinated with four nitrogen atoms of parent ligand L4, two oxygenatoms of NOs" ion and two other oxygen atoms of the other NOs" ion, to formeight coordination center of deformed tetragonal bipyramid;(3) Cd2+coordinated with four nitrogen atoms of parent ligand L4, twooxygen atoms of NCV ion and two oxygen atoms of the other NO3- ion, to formeight coordination center of deformed tetragonal bipyramid;(4) Ni2+coordinated with four nitrogen atoms of parent ligand L4, two oxygen atoms of SO4 2- ion, to form six coordination center of deformed triangular prism.In addition, the results obtained indicated that the oxygen atom of pendant-arm of compound L3 did not take part in the coordination with metal cations as well as the sulfur atom pendant-arm of compound L4.