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为了考察金属卟啉与含氮杂环化合物之间的轴向配位作用,本文采用密度泛函理论方法研究了中心金属分别为铁、锰、钴的3种金属卟啉与咪唑及吡啶2种轴向配体之间形成的配位络合物,从几何结构、相互作用能方面考察了配位络合物的稳定性、并从电荷和前线分子轨道能级方面解释了所形成配位络合物稳定性的差异。计算结果表明,具有不同中心金属离子的卟啉与不同轴向配体之间的配位作用也不同,卟啉中心金属的正电性越强,其与咪唑及吡啶所形成的配位络合物越稳定。3种金属卟啉中,铁卟啉中心金属具有较多的正电荷,更易与咪唑或吡啶发生轴向配位作用形成稳定的配位络合物。与吡啶相比,咪唑与金属卟啉之间的配位作用更强,形成的配位络合物更稳定。
In order to investigate the axial coordination between metalloporphyrins and nitrogen-containing heterocyclic compounds, three kinds of metalloporphyrins with iron, manganese and cobalt as the central metal and two kinds of imidazole and pyridine were studied by using density functional theory Coordination complex formed between the axial ligands, from the geometric structure, interaction energy of the coordination complex was investigated stability, and from the charge and frontier molecular orbital energy level explained the formation of coordination network Differences in compound stability. The calculated results show that the coordination between porphyrins with different central metal ions and different axial ligands is also different. The positive electropositivity of the center metal of porphyrin is stronger than that of the coordination metal complex formed by imidazole and pyridine The more stable the thing. Of the three kinds of metalloporphyrins, the central metalloporphyrin possesses more positive charges, which makes it easier to coordinate with imidazole or pyridine to form a stable coordination complex. Compared with pyridine, the coordination between imidazole and metalloporphyrin is stronger and the formed coordination complex is more stable.