【化学工程与工艺专业】【毕业设计+开题报告+文献综述】四氮杂二氢卟啉和四氮杂四氢卟啉过渡金属配合物的结构和电子光谱的理论研究.doc

（20 届） 毕业设计 四氮杂二氢卟啉和四氮杂四氢卟啉过渡金属配合物的结构和电子光谱的理论研究　 摘要: 氮杂卟啉与酞菁一样，由于具有紧稠的大环结构和可离域化的共轭 π-电子体系，以及高的耐热、耐光、耐酸、耐碱稳定性和优异的电子功能，而日益受到人们的重视。目前，特别是金属四氮杂卟啉作为仿生催化剂在温和条件下模拟含铁氧化酶特性氧化降解水中有毒有机污染物，显示出了其广阔的应用前景。 论文理论研究了四氮杂二氢卟啉、四氮杂四氢卟啉的Co、Ni、Cu、ZnCβ=Cβ。键氢化倾向于增加非平面变形。 关键词: 四氮杂卟啉；密度泛函理论；氢化卟啉。 Abstract: The two cornerstones in tetrapyrrolic macrocycle systems are porphyrins and tetraazaporphyrins (also called as porphyrazines), which include phthalocyanines. As porphyrins and phthalocyanines, porphyrazines have a closely fused macrocyclic skeletonwith an extendedly, delocalizedly conjugated macrocyclic π-system and high stabilities for heat and light, acid-resistance, base-resistance and excellent performance of electron etc., and aving more and more attracted considerable attention from scientists of many fields.Especially, metal-porphyrazines now display an extensively applicable prospects for degrading toxic organic pollutants in the wastewater by mimicking the oxidative characteristics of iron-containing oxygenase enzymes under mild conditions. We investigated the ground state structures and electronic spectra for the cobalt，nickel, copper and zinc complexes of tetraazachlorin and tetraazabacteriochlorin with the density functional theory. The corresponding metal complexes of chlorin and baeterioehlorin were also studied for comparison.Seven of the total sixteen studied species were found to display non-planar ruffling deformation.It was revealed that meso-teraaza substitution tends to reduce the degree of the deformation while the hydrogenation of the Cβ=Cβ bond tends to increase it. Keywords: tetraazaporphyrin；DFT；hydroPorphyrin.摘要: I 1 绪论 1 1.1 前言 1 1.2 四氮杂卟啉的研究概况 2 1.2.1 四氮杂卟啉研究进展 2 1.2.2 研究背景与意义 4 2 实验部分 5 2.1 研究内容 5 3. 结果与分析 6 3.1 基态几何结构 6 3.1.1 非平面变形 6 3.1.2 Np…Np与Np… Np原子间距离 10 3.1.3 吡咯环 11 3.2 电荷分布 12 3.3 电子激发态 13 4.结论 19 致谢 20 参考文献 21 1 绪论 前言 四氮杂卟啉与酞菁一样，由于具有紧稠的大环结构和可离域化的共轭 π-电子体系，以及高的耐热、耐光、耐酸、耐碱稳定性和优异的电子功能，而日益受到人们的重视。phthalocyanine，简称 Pc，见图1.1）最早是由 Braun 教授和Tc