物理化学学报 >> 1996, Vol. 12 >> Issue (03): 202-207.doi: 10.3866/PKU.WHXB19960303

研究论文 上一篇    下一篇

质子化和脱质子化对酞菁光谱的影响

刘剑波, 赵瑜, 赵福群, 张复实, 唐应武, 宋心琦, 周福添   

  1. 清华大学化学系，北京 100084|香港理工大学应用生物及化学科技学系
  • 收稿日期:1995-05-16 修回日期:1995-07-06 发布日期:1996-03-15
  • 通讯作者: 刘剑波

Effects of Protonation and Deprotonation on Phthalocyanine's Spectra

Liu Jian-Bo, Zhao Yu, Zhao Fu-Qun, Zhang Fu-Shi, Tang Ying-Wu, Song Xin-qi, Zhou Fu-Tian   

  1. Department of Chemistry,Tsinghua University,Beijing 100084|Department of Applied Biology and Chemical Technology,Hong Kong Polytechnic University,Hong Kong
  • Received:1995-05-16 Revised:1995-07-06 Published:1996-03-15
  • Contact: Liu Jian-Bo

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摘要：

系统地研究了四异丙氧基酞菁的质子化和脱质子化对吸收和发射光谱的影响．研究表明，三氟乙酸可对酞菁分子连续质子化，分别生成[H2Pc(OiPr)4•H+]+和[H2Pc(OiPr)4•2H+]2+而硫酸可使酞菁形成[H2Pc(OiPr)4•4H+]4+. 此外，NaOH／EtOH可使酞菁分子脱质子化生成[Pc(OiPr)4]2-，反应一步完成，表明分子中的两个吡咯-NH-同步酸解，质子化可使吸收光谱的Q带和荧光发射峰显著红移，证明酞菁激发态的碱性强于基态．对这些实验现象，利用四轨道电子跃迁模型作了合理的解释．

关键词: 酞菁, 质子化, 托质子化

Abstract:

The absorption and emission properties of H2Pc(OiPr)4 were studied as a function of protonation and deprotonation. Stepwise protonation using TFA yielded [H2Pc(OiPr)4•H+]+ and [H2Pc(OiPr)4•2H+]2+. [H2Pc(OiPr)4•4H+]4+ can be formed in concentrated sulfuric acid. Additionally, the NaOH/EtOH can deprotonate H2Pc(OiPr)4 to [Pc(OiPr)4]2-, the acid-dissociation of the two pyrrolic -NH occurred synchronous. Manifest bathochromic shifts of the Q band absorption for each bound proton indicated the basicity of phthalocyanine in the excided state is stronger than that in the ground state. In order to explain the experimental phenomena, the effects of protonation and deprotonation on MOs were proposed.

Key words: Phthalocyanine, Protonation, Deprotonation