摘要
结合密度泛函B3LYP和含时密度泛函TD-B3LYP方法在PCM溶剂模型下对拓展卟啉及锌、镍双金属离子配合物的电子结构、分子轨道、紫外吸收、荧光发射光谱等进行了理论研究.结果表明拓展卟啉hexaphyrins与Ni^(2+)、Zn^(2+)均可以形成较稳定的配合物,过渡金属离子对分子中N原子的配位具有一定的选择性,配合物hexaphyrinsNi^(2+)产生了更好的共轭效应,而配合物hexaphyrins-Zn^(2+)中电子转移能力更强.紫外吸收与荧光发射的研究表明它们具有独特的发光性能,其激发态的配合物hexaphyrins-Ni^(2+)在强极性溶剂作用下产生了更佳的荧光效应,这为拓展卟啉配合物制备荧光发光材料做了较好的理论解释,也为荧光材料的进一步合成与制备发挥了积极的指导意义.
The electronic structure, molecular orbital, UV absorption, and fluorescence emission spectra of hexaphyrins, hexaphyrins-Ni2＋ and hexaphyrins-Zn2＋ were studied by using density functional B3LYP and time-dependent density functional theory TD-B3LYP method in PCM solvent model. The results show that hexaphyrins can form stable complexes with Ni2 ＋ or Zn2 ＋ , and the transition metal select some nitrogen atoms to coordinate in themolecule. The hexaphyrins-Ni complex produces a better conjugation effect, but hexaphyrins-Zn complex is stronger. They all have a unique luminescent the electron transfer ability of the property by UV absorption and fluorescence emission peak simulation, and the excited state of hexaphyrins-Ni2＋ complex show a better fluorescence effect in a strong polar solvent. This work can explain the reason of these complexes can be prepared into the fluorescent luminescent materials, which also can guide the further synthesis of new fluorescent material.
作者
龙威
符志鹏
李紫艳
黄银飞
Long Wei Fu Zhipeng Li Ziyan Huang Yinfei(Research Institute of Journal, University of South China, Hengyang Hunan 421000 School of Chemistry and Chemical Engineering, University of South China, Hengyang Hunan 421001)
出处
《首都师范大学学报（自然科学版）》
2017年第4期45-53,共9页
Journal of Capital Normal University：Natural Science Edition
基金
衡阳市科技局项目(2015KJ09)资助
关键词
拓展卟啉
密度泛函
含时密度泛函
发光材料
hexaphyrins, density functional, time-dependent density functional, luminescence material
