高等学校化学学报

高等学校化学学报 ›› 2002, Vol. 23 ›› Issue (8): 1562.

• 研究论文 • 上一篇    下一篇

四苯基卟啉质子化结构变化的理论研究(Ⅱ)——五氟苯基及吡咯环上氟的取代基效应

黄晓芬, 马思渝, 刘若庄   

  1. 北京师范大学化学系, 北京 100875
  • 收稿日期:2001-07-03 出版日期:2002-08-24 发布日期:2002-08-24
  • 通讯作者: siyuma50@hotmail.com
  • 作者简介:马思渝(1946年出生),男,教授,主要从事理论化学和计算化学研究.E-mail:siyuma50@hotmail.com
  • 基金资助:

    国家自然科学基金(批准号:29992590-1)资助

Theoretical Studies on the Structural Change of the N'-Protonated Tetraphenylporphyrin(Ⅱ) The Effects of the Substituting Groups Fluorines

HUANG Xiao-Fen, MA Si-Yu, LIU Ruo-Zhuang   

  1. Department of Chemistry, Beijing Normal University, Beijing 100875, China
  • Received:2001-07-03 Online:2002-08-24 Published:2002-08-24

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摘要： 卟啉的衍生物在DNA螺旋中的嵌入并堆积具有高选择性.为考察5,10,15,20-四(五氟苯基)卟啉(TF5-PPH2)和2,3,7,8,12,13,17,18-八氟-5,10,15,20-四(五氟苯基)卟啉(F28TPPH2)中F取代基对质子化卟啉结构的影响,在四苯基卟啉研究的基础上,用半经验的AM1MO方法,并进行合理的对称性限制,计算了TF5-PPH2和F28TPPH2及其质子化二酸(TF5-PPH42+)和(F28TPPH42+)的几种可能的构型.结果表明,由于F取代基的影响,质子化过程中的结构、键电荷布居和前线分子轨道均有明显的变化,二者的质子化二酸与溶液质子的快速交换作用也都变得更加困难.

关键词: 5, 10, 15, 20-四(五氟苯基)卟啉, 2, 3, 7, 8, 12, 13, 17, 18-八氟-5, 10, 15, 20-四(五氟苯基)卟啉, N'-质子化二酸, 构型变化

Abstract: With the symmetry being reasonably restricted, the semi empirical method of AM1 MOis used to calculate the geometries of 5, 10, 15, 20-tetrakis(pentafluorophenyl)porphyrin(TF5PPH2) and 2, 3, 7, 8, 12, 13, 17, 18 octafluoro 5, 10, 15, 20-tetrakis(pentafluorophenyl)porphyrin(F28TPPH2) and their Nprotonated diacids(TF5PPH42+ and F28 TPPH42+) which all are kinds of important porphyrin derivatives. Moreover, the configurational change in protonation process and the probable influence to molecular aggregation conducted by the change are discussed by the means of structure analysis, population analysis and frontier orbital analysis.

Key words: Tetrakis(pentafluorophenyl)porphyrin(TF5-PPH2), 2,3,7,8,12,13,17,18 Octafluoro5,10,15,20-tetrakis(pentafluorophenyl)porphyrin(F28 TPPH2), N Protonated diacids, Configurational change

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