物理化学学报 >> 1997, Vol. 13 >> Issue (01): 11-15.doi: 10.3866/PKU.WHXB19970103

研究论文 上一篇    下一篇

新型卟啉-酞菁二元分子内光物理过程的研究

李希友,田宏建,周庆复,许慧君   

  1. 中国科学院感光化学研究所，北京 100101
  • 收稿日期:1996-06-02 修回日期:1996-09-02 发布日期:1997-01-15
  • 通讯作者:

The Photophysical Process of A New Kind of Porohyrin-Phthalocyanine Heterodimer

Li Xi-You,Tian Hong-Jian,Zhou Qing-Fu,Xu Hui-Jun   

  1. Institute of Photographic Chemistry,Academia Sinica,Beijing 100101
  • Received:1996-06-02 Revised:1996-09-02 Published:1997-01-15
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摘要：

合成了以哌嗪连接的含卟啉-酞菁的双发色团分子，测定了它的吸收光谱，荧光光谱和荧光寿命.并计算了在不同溶剂中两发色团之间的能量传递效率ФEnT和电子转移效率ФET.结果表明：在非极性溶剂苯中，两发色团之间的光物理过程以激发态单线态能基传递为主（ФEnT80％）.而在极性溶剂DMF中，则以电子转移为主（ФET69.8％）该二元化合物在DMF中的电子转移效率明显高于我们以前合成的以氧或柔性链连接的二元化合物.这可能是由于在DMF中，哌嗪以船式构象存在，两个发色团呈较固定的，相互平行的面对面构象.从CPK分子模型可以算出卟啉环和酞菁环中心至中心的距离为3.56Å.

关键词: 哌嗪, 二元化合物, 能量传递, 光诱导电子转移

Abstract:

Intramolecular energy-transfer and electron-transfer of porphyrin-phthalocyanine heterodimer, linked by piperazine, were investigated by absorption and fluorescencc spectroscopy. The efficiency of energy transfer(ФEnT) and electron transfer (ФET) were calculated. The results indicate that: In benzene, the main photophysical process is excited singlet-singlet energy transfer, while in DMF photoinduced electron transfer predominant. The ФET of this heterodimer in DMF is bigger than that of porphyrin-phthalocyanine heterodimers linked by oxygen or flexible chains. This may be ascribed to the "boat-form" conformation of piperazine, According to the CPK molecular model, porphyrin and phthalocyanine are held together in a face to face way, and the center to center distance between two macrorings is about 3.56 Å . It is suggested that conformational changes from "chair form" to "boat form" occurred subsequent to optical excitation in DMF.

Key words: Piperazine, Heterodimer, Intramolecular energy transfer, Photoinduced electron transfer