六元扩展卟啉的Zn^(2+),Cd^(2+),Hg^(2+)单金属配合物的光电性质的理论研究

Theoretical investingation on electronic transition of [26]hexaphyrin(1.1.1.1.1.1) and their Zn^(2+),Cd^(2+) and Hg^(2+) mono-metal complexes

通过定域密度矩阵方法和含时密度泛函方法研究了六元扩展卟啉及其Zn,Cd和Hg单金属配合物的光电性质.通过计算得到扩展卟啉HP同金属Zn2+,Cd2+和Hg2+发生配位时,分子趋于平面化.配合物在Q带有弱得吸收峰,它们随着中心金属的原子序数的增加产生了红移.在B带有强吸收峰,其特征峰主要来自于中心金属离子的d轨道和同金属配位的C原子所处的吡咯环以及吡咯环两侧的meso-C原子上的苯基的参与.对于扩展卟啉极其配合物,定域密度矩阵方法也可以很好的预测光谱和电子跃迁性质.

The electronic absorption spectra of Zn2＋,Cd2＋ and Hg2＋ mono-metal complexes of hexaphyrin（1.1.1.1.1.1） were systematically investigated using the localized density matrix（LDM） method and time-dependent density functional theory（TD-DFT）.The results show that complexes are more co-planarity when HP coordinates with Zn2＋,Cd2＋ and Hg2＋ ions.The absorption characteristics represent weak Q-like bands.In addition,the introduction of group 12 transition metals（Ⅱ） leads to red shifts by adding central metal atomic number.The absorption characteristics of strong B-like bands exhibit ligand-to-metal charge transfer characteristics due to contributions from phenyl rings in the meso-carbons.The LDM method is a reliable approach for determining the electronic transition properties of the complexes and substantially reduces the computational cost.