物理化学学报 >> 2007, Vol. 23 >> Issue (10): 1594-1598.doi: 10.3866/PKU.WHXB20071019

研究论文 上一篇    下一篇

取代基对卟吩结构和性质的影响

林英武; 王中华; 聂长明; 倪峰云   

  1. 南华大学化学化工学院, 湖南 衡阳 421001; 复旦大学化学系, 上海 200433
  • 收稿日期:2007-04-05 修回日期:2007-05-17 发布日期:2007-10-01
  • 通讯作者: 林英武 E-mail:linlinying@hotmail.com

Effects of Substitution on the Structure and Property of Porphin

LIN Ying-Wu; WANG Zhong-Hua; NIE Chang-Ming; NI Feng-Yun   

  1. College of Chemistry and Chemical Engineering, Nanhua University, Hengyang 421001, Hunan Province, P. R. China; Department of Chemistry, Fudan University, Shanghai 200433, P. R. China
  • Received:2007-04-05 Revised:2007-05-17 Published:2007-10-01
  • Contact: LIN Ying-Wu E-mail:linlinying@hotmail.com

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摘要： 运用密度泛函理论(DFT) B3LYP/6-31G(d, p)方法, 对卟吩及其被取代基—CH=CH2、—COCH3、—CHOHCH3、—CHNH2CH3或—CHSHCH3所修饰后的分子构型进行了优化. 同时, 对其电子吸收光谱与核磁共振氢谱也进行了量化计算. 结果表明, 这些取代基有着各自不同的空间构象, 对卟吩环的整体结构没有很大的扰动. 然而, 它们重新调整了卟吩环中原子电荷的分布, 改变了前线分子轨道(LUMO-HOMO)能隙, 结果导致卟吩的吸收光谱与1H NMR均发生了相应的改变.

关键词: 卟吩, 取代基, 密度泛函理论, 吸收光谱, 核磁共振氢谱

Abstract: The molecular geometries of porphin and those modified with —CH=CH2, —COCH3, —CHOHCH3, —CHNH2CH3, or —CHSHCH3 groups were optimized at the B3LYP/6-31G (d, p) level of density functional theory (DFT). At the same time, their absorption spectra and 1H NMR were also calculated. The results illustrated that these substitution groups had differential spatial positions and did not disturb the structure of porphin extremely. Meanwhile, they have re-adjusted the contribution of atomic charges of porphin and then have changed the LUMO-HOMO energy gaps of porphin. As a result, the absorption spectra and 1H NMR were changed accordingly.

Key words: Porphrin, Substitution, Density functional theory, Absorption spectrum, 1H NMR