物理化学学报 >> 1996, Vol. 12 >> Issue (05): 423-428.doi: 10.3866/PKU.WHXB19960508

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降冰片二烯衍生物光敏异构化反应的机理研究

王雪松,张宝文,曹怡   

  1. 中国科学院感光化学研究所，北京 100101
  • 收稿日期:1995-10-09 修回日期:1995-12-13 发布日期:1996-05-15
  • 通讯作者: 曹怡

A Mechanism Study of Sensitized Photoisomerization of Norbornadiene Derivatives

Wang Xue-Song,Zhang Bao-Wen,Cao Yi   

  1. Laboratory of Photochemistry,Institute of Photographic Chemistry,The Chinese Academy of Sciences,Beijing 100101
  • Received:1995-10-09 Revised:1995-12-13 Published:1996-05-15
  • Contact: Cao Yi

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摘要：

利用甲基咔唑为光敏剂，实现了三个降冰片二烯衍生物的光诱导价键异构化反应，荧光猝灭、化学诱导动态核极化（CIDNP）以及热力学讨论都支持电子转移敏化机理，有关量子效率的计算表明单重态电子转移机制对光异构化反应的贡献远大于三重态能量传递机制．此外还探讨了光异物化反应中的溶剂极性效应.

关键词: 降冰片二烯衍生物, 甲基咔唑, 光异构化反应, 电子转移, 能量传递, 溶剂极性效应

Abstract:

The photoinduced valence isomerizations of three kinds of norbornadiene derivatives were performed under the sensitization of N-methylcarbazole. Fluoresecence quenching, chemically induced dynamic nuclear polarization (CIDNP) and thermodynamic discussion all support a mechanism involving electron transfer. The calculation of quantum yields indicates that the singlet electron transfer makes far more contributions to the photoisomerization than the triplet energy transfer. Additionally, the influence of solvent polarity on the photoisomerizations was also discussed.

Key words: Norbornadiene derivatives, N-methylcarbazole, Photoinduced valence isomerization, Electron transfer, Energy transfer, Effect of solvent polarity