Synthesis, Characterization And Crystal Structures Of Polyamine Crown Ether Metal Complexes

This thesis reports the contents as follows.1. The recent advances on polyamine crown ethers, their derivatives and their complexes are reviewed, especially on their synthesis and application studies.2. By the three-step reactions, including substitution, cyclization, and reduction, the ligand,1,4,23,26,29,48-hexaaza-6,9:16,19:31,34:41,44-tetrabenz-o-12,15,37,40-tetraoxa-cyclodotetracontane (L), was obtained. Four new com-plexes,[Cd2(OCOPh)4L](C4H8O2)(H2O)2.5(1),[Cd2(o-OCOPhOH)4L](DMF)2(2),[Cd2(H2O)6L](p-OSO2PhCH3)4(H2O)2(3),[Cu2(OCOPh)4L](C4H8O2)2(H2O)4(4), were synthesized by reaction of L with Cd(OCOPh)2, Cd(o-OCOP hOH)2, Cd(p-OSO2PhCH3)2, and Cu(OCOPh)2, respectively. The crystal structu-res of these complexes were determined by X-ray diffraction. The results show-ed that both complex (1) and complex (2) are dinuclear and six-coordinated co-mpounds with octahedral geometry, belonging to the triclinic system and the sp-ace group P-1, complex (3) is dinuclear six-coordinated compound with octah-edral structure, belongs to the monoclinic system and the space group P2(1)/c. Whereas in the structure of complex (4), it is a dinuclear five-coordinated compound with a trigonal bipyramid geometry, which crystallized in triclinic system and space group P-1.3. Five new complexes,[Zn2(OCOCOPh)4L](CH3OH)2(H2O)1.5(5),[Zn2(o-OCOPhOH)4L](DMF)2(6),[Zn2(m-OCOPhOH)4L](DMSO)4(7),[Zn2(p-OCOPhOH)4L](H2O)2(8),[Zn2(p-OSO2PhCH3)4L(ONC3H7)2](DMF)4(C4H8O2)(9), were prepared by the reactions of L with several zinc salts. The single crystals of these complexes had been obtained and characterized by X-ray diffraction. The results indicate that complex (5) is dinuclear in monoclinic system and space group P2(1)/c with five-coordinated trigonal bipyramidal geometry, whereas other complexes, including complex (6), complex (7), and complex (8) are dinuclear five-coordinated compounds in the triclinic system and the space group P-1, with trigonal bipyramidal geometry. Complex (9) is dinuclear six-coordinated compound with octahedral structure, belongs to the triclinic system and the space group P-1. The network structure of the eight complexes is constituted via intermolecular and intramolecular hydrogen bonds, π-π interactions.4. Finally, the conclusions of this study were made and the development of the research work of the future was summarized. Future applications are prospected with the expectation of more significant developments in the fields of medicine, life science, material science and environmental science. The work provides good candidates for further studies in the fields of medicine, life science, material science and environmental science and deserves to be extended to other macrocyclic complexes on attempting to study coordination effects and to establish relationships.