Synthesis, Characterization And Crystal Structures Of Macrocyclopolyamine Crown Ether And Its Complexes

This thesis mainly described as follows:1, A macrocyclicpolyamine ligands,1,4,23,26,29,48-hexaaza-6,9:16,19:31,34:41,44-tetrabenzo-12,15,37,40-tetraoxa-cyclodotetracontane (L), via three-steps reactions of substitution, cyclization and reduction, synthetized with hydroxyl benzaldehyde,1,2-dichloroethane and divinyl three amine,2, The Cu(Ⅱ) compounds and Ni(Ⅱ) compound,{[Cu2(SO3PhCH3)2L(DMF)2](SO3PhCH3)2(DMF)2(H2O)2}n (1),{[Cu2L(CH3CO2)2](CH3CO2)2(C4H8O2)(H2O)5}n (2),{[Ni2(CH3CO2)4L](C4H8O2)10H2O}n (3) were synthesized by solvent reactions and diffusion processes from L and Cu(CH3phSO3)2, Cu(CH3CO2)2·H2O, Ni(CH3CO2)2-4H2O, respectively. These complexes were charaterized by single crystal X-ray diffraction. The complexes (1),(2) and (3) belong to triclinic crystal system with space group Pi and all are di-nuclear. The Cu(II) ion in complexe (1) is coordinated by three N-atoms from one ligand, one O-atom from SO3PhCH3(I) and one O-atom from CH3CO2(Ⅰ), forming an irregular CuN3O2pentagonal pyramidal geometry. The Cu(II) ion in complex (2) is coordinated by three N-atoms from ligand, one O-atom from one of the CH3CO2(Ⅰ)and by one O-atom of the other CH3CO2(Ⅰ), forming an irregular CuN3O2pentagonal pyramidal geometry. The Ni(Ⅱ) ion in complexe (3) is coordinated by three N-atoms from the ligand, by two O-atom from one of the CH3CO2(Ⅰ) and by one O-atom of the other CH3CO2(Ⅰ), forming an irregular NiN3O3distorted octahedra. One1,4-dioxane molecule is contained in the crystal lattices of complexes (2) and (3). All complexes show hydron-bonds in their molecules.With the reaction of L and hydrochloric acid, a supermolecule compound,[L2(Cl)1414H2O]n (4) was obtained and its structure was characterized by single crystal X-ray diffraction method. Complexes (4) belongs to triclinic crystal system with space group Pi. The crystal cell parameters are:a=6.0909(12), b=13.185(3), c=35.734(7); a=87.97(3), β=88.84(3)γ=85.93(3); V=2860.3. The molecules of complexe (4) stack into a three-dimension structure by hydrogen-bonds.3, The sandwish mononuclear cobalt(Ⅱ) and nickel(Ⅱ) complexes {[Co2Lt4](H20)10(Cl)4}n (5) and{[Ni2Lt4](H2O)2(CH3PhSO3)4}n (6) were obtained by reaction of CoCl2-6H2O and Ni(CH3PhSO3)2with4’-phenyl-terpyridine (Lt), via hydrothermal methods. These complexes were charaterized by single crystal X-ray diffraction. Complexes (5) and (6) belong to triclinic crystal system with space group Pi. Each Co(Ⅱ) or Ni(Ⅱ) ion is coordinated by six N-atoms from two different ligands, forming irregular CoN6and NiN6distorted octahedral. In complexe (5), its octahedral geometry is consisted of a plane (N3N4N5N6) and the apical positions were occupied by N1and N2. In complexe (6), the apical positions were occupied by N3and N4. The complexes have different conformations of coordination. Both of the two complexes show a large number of hydron-bonds in their strutures.