Study On Synthesis, Crystal Structures And Properties Of Azamacrocyclic Metal Complexes

The azamacrocyclic coordination complexes of transition metal have distinctivestructures and properties, which have an important theoretical significance and broadapplications values in life science, development of new materials and supramolecularself-assembly. This thesis mainly includes the following points:1. Two series of azamacrocyclic complexes of transition metal were designedand synthesized. Four complexes were new compounds, and were characterized bysingle-crystal X-ray diffraction analyses, UV-Vis, IR, EA and MS.（1） Two new14-membered hexaaza macrocyclic complexes [NiL1]（ClO₄）₂（1）and [CuL1]（ClO₄）₂（2） have been synthesized by metal ion template. In complex1,the nickel（II） ion is four-coordinated with four nitrogen atoms from the macrocyclicligand and forms a square-planar coordination geometry. In complex2, thecopper（II） ion is six-coordinated with four nitrogen atoms from the macrocyclicligand and two oxygen atoms from the two perchlorate anions, and forms anoctahedron coordination geometry.（2） The hexaaza26-member macrocyclic ligand L⁰（L⁰=Bis-p-xylylBISDIENSchiff base）acting as starting material was hydroxylated and deoxidated, and a hexaaza26-member macrocyclic ligand L²containing two hydroxypropyl branched chains（L²=6,19-bis（2-hydroxypropyl）-3,6,9,16,19,22-hexaaza-tricyclo-[22.2.2.211,14]triaconta-11,13,24,26,27,29-hexaene） was prepared, by which complex3and4weresynthesized.2. The DNA-binding modes of complexe1,2,3,4were studied by UV-VISspectrophotometry, fluorescence spectroscopy, viscosity measurements and agarosegel electrophoresis experiments. The results indicate that complexe1and2werecombined with DNA by electrostatic mode，while complexe3and4could interactwith DNA by insert mode. Complex3and4can cleave plasmid PUC18DNAefficiently.3. Complex3and4acting as active centers of model compounds for the hydrolyticmetalloenzyme have been conducted to investigate the kinetics of catalytic hydrolysison p-nitrophenyl acetate. A possible catalytic mechanism was proposed. Theresults show that the hydrolysis process is controlled by an acid-base equilibrium. As to complex3and4, the constants of hydrolysis rate were respectively0.098mol^-1·L·s^-1and0.082mol^-1·L·s^-1.