Synthesis And Property Research Of Nitrogenous Complexes

This thesis includes 4 chapters. The first chapter introduces the research background, and focuses on the development of complexes ligated by mixed-ligands, such as 1, 3, 5-benzene tricarboxylic acid with nitrogenous heterocyclicle, and benzimidazole with imidazole. Meanwhile, the research situation of macrocycle compound application in metalloporphyrin axial coordination and oxidative catalysis are also investigated as well.In chapter 2, three novel coordination polymer crystals of Zn (II) and Ag (I) with 1,3,5-benzene tricarboxylic acid and benzimidazole or imidazole ligands have been successfully assembled, including (1) {Zn₃[(btc)₂(bzim)₃]}_n, (2){Ag₂[(Hbtc)(im)]}_n and (3) {[Ag₃(btc)(im)]·H₂O}_n. Complex 2 and 3 were synthesized with the same ligand amount and reactant ratio, but with different silver salts (Ag₂SO₄ for complex 2 and AgNO₃ for complex 3), and as result, different crystal architectures were obtained. Finally, these coordination polymers had been characterized by element analysis, infrared spectra, luminescence spectra, X-ray single crystal diffraction and as well as thermodynamics analysis.In chapter 3, some metalloporphyrins, including zinc(II) meso–tetra (4-hydroxyphenyl) porphyrin {Zn(II)THPP}, iron(III) meso–tetra (4-hydroxyphenyl) porphyrin chloride {Fe(III)THPPCl} and cobalt(II) meso -tetra (4-phenyl) porphyrin {Co(II)TPP} had been synthesized. Then, select histidine(His), tryptophan(Trp), glutamic acid(Glu), imidazole(Im) and benzimidazole(Bzim) as axial ligands, the axial coordination influences on those metalloporphyrins were investigated by using of UV-Vis spectrophotometry. As well as the fluorescent comparing and changing spectra of Zn(II)THPP, without and with the axial ligands, were also examined.In chapter 4, an oxidation from p-cresol to p-hydroxybenzaldehyde (PHBA) over cobalt (II) meso-tetra (4-methoxyphenyl)porphyrin {Co(II)T(p-OCH₃)PP} catalyst was examined primarily. The reaction condition was optimized as: p-Cresol (4.3g, 0.04mol), sodium hydroxide (6.0g, 0.15mol), and Co(II)T(p-OCH3)PP (0.0008g, 1×10^-6mol), were mixed together for refluxing 6h at 80℃with yielded of PHBA reaching 24.7%.