Acta Phys. -Chim. Sin. ›› 1996, Vol. 12 ›› Issue (01): 12-17.doi: 10.3866/PKU.WHXB19960104

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Study on the Intramolecular Electron Transfer of TTP-(CH2)n-Pc

CHEN Jian-Xin, TIAN Hong-Jian, ZHANG Hong-Hao, ZHOU Qiang-Fu, HU Hui-Jun, XU Guang-Zhi   

  1. State Key Laboratory for Structural Chemistry of Unstable and Stable Species,Institute of Chemistry,Chinese Academy of Sciences,Beijing 100080;Institute of Photographic Chemistry,Chinese Academy of Sciences,Beijing 100101
  • Received:1994-11-05 Revised:1995-05-09 Published:1996-01-15
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Abstract:

The intramolecular electron transfer of TTP-(CH2)n-Pc was studied by means of time correlated single-photon counting method. When the Pc subunit of the compound is excited, the fluorescence of the compound is quenched by intramolecular electron transfer and the electron transfer is most favorable in the compound with n=4. When the TTP subunit of the compound is excited, the fluorescence decay of the compound will be biexponential, which shows the existence of an electron transfer process. Some kinetic parameters were derived from the experimental data. With n increasing, the activation energy and the reorganization energy increases whereas the electron transfer rate decreases. Moreover, the free enthalpy change of electron transfer reaction △G CS and the charge-separated rate kCS are in the order of:
△G CS (5) >△G CS (3) >△G CS (4) >△G CS (2)
kCS (2) >kCS (3) >kCS (4) >kCS (5)
The difference between the order of △G CS and of electron transfer rate can be interpreted according to Marcus theory.

Key words: Porphyrin-phthalocyanine, Electron transfer, Time correlated single photon couting, Fluorescence