物理化学学报 >> 2016, Vol. 32 >> Issue (8): 1983-1989.doi: 10.3866/PKU.WHXB201604222

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β位取代基对咔咯锰(Ⅴ)氧配合物电子吸收光谱的影响

陈华彬1,章小慧1,龚丽珍1,何婧1,许旋1,徐志广1,*(),刘海洋2,*()   

  1. 1 华南师范大学化学与环境学院,教育部环境理论化学重点实验室,广州510006
    2 华南理工大学化学系,广州510641
  • 收稿日期:2016-01-11 发布日期:2016-07-29
  • 通讯作者: 徐志广,刘海洋 E-mail:chzgxu@scnu.edu.cn;chhyliu@scut.edu.cn

Effect of β-Substituents on the Electronic Absorption Spectra of Manganese(Ⅴ)-oxo Corrole Complexes

Hua-Bin CHEN1,Xiao-Hui ZHANG1,Li-Zhen GONG1,Jing HE1,Xuan XU1,Zhi-Guang XU1,*(),Hai-Yang LIU2,*()   

  1. 1 Key Laboratory of Theoretical Chemistry of Environment, Ministry of Education, School of Chemistry and Environment, South China Normal University; Guangzhou 510006, P. R. China
    2 Department of Chemistry, South China University of Technology, Guangzhou 510641, P. R. China
  • Received:2016-01-11 Published:2016-07-29
  • Contact: Zhi-Guang XU,Hai-Yang LIU E-mail:chzgxu@scnu.edu.cn;chhyliu@scut.edu.cn

摘要:

采用含时密度泛函理论(TDDFT)和B3LYP方法对一系列β位咔咯锰(Ⅴ)氧配合物的几何结构、前线轨道、自然键轨道和电子吸收光谱进行了计算。并探讨了β位取代基对咔咯锰(Ⅴ)氧配合物电子吸收光谱的影响。结果显示β位取代基效应中的空间效应是能导致该体系电子吸收光谱Soret带和Q带红移。β位取代基的空间位阻大时,导致配合物的咔咯环产生严重扭曲,引起Soret带和Q带吸收峰的ΔE能隙减小,导致Soret带和Q带发生红移。

关键词: 咔咯锰(Ⅴ)氧配合物, 电子吸收光谱, TDDFT, 取代基

Abstract:

Time-dependent density functional theory (TDDFT) calculations using the B3LYP method were used to investigate the effect of β-substituents on the electronic absorption spectra of a series of manganese(Ⅴ)-oxo corrole complexes. The geometries, frontier molecular orbitals, and energies of the complexes were analyzed. The calculated results indicate that the steric effect of the β-substituents is the factor controlling the red-shift of the Soret bands and Q bands in these complexes. The sterically hindered β-substituents cause twisting of the corrole ring structure, which leads to reduced orbital energy gaps and a red-shift of the Soret bands and Q bands.

Key words: Manganese(Ⅴ)-oxo corrole, Electronic absorption spectrum, TDDFT, Substituent

MSC2000: 

  • O641