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Electron Transfer in Oligothiophene-Bridged Bisporphyrins

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Martin Regehly^†, Tianyu Wang^§, Ulrich Siggel*^‡, Jürgen H. Fuhrhop^§ and Beate Röder*^†

Institut für Physik, Photobiophysik, Humboldt Universität, Newtonstr. 15, D-12489 Berlin, Germany; Institut für Chemie, Max-Volmer Labor, Technische Universität Berlin, Strasse des 17. Juni, D-10623 Berlin; and Institut für Chemie und Biochemie, Organische Chemie, Freie Universität Berlin, Takustr. 3, D-14195 Berlin, Germany

J. Phys. Chem. B, 2009, 113 (8), pp 2526–2534

DOI: 10.1021/jp808052u

Publication Date (Web): February 3, 2009

* Corresponding authors: Tel +49 30 2093 7625; Fax +49 30 2093 7666; e-mail ulsiseab@mailbox.tu-berlin.de (U.S.), roeder@physik.hu-berlin.de (B.R.)., †

Humboldt Universität.

, ‡

Technische Universität Berlin.

, §

Freie Universität Berlin.

Present address: CAS Key Laboratory of Colloid, Interface and Chemical Thermodynamics, Institute of Chemistry, The Chinese Academy of Sciences, Beijing 100080, P.R. China.

Section:

Radiation Chemistry, Photochemistry, and Photographic and Other Reprographic Processes

Abstract

Oligothiophene-bridged zinc−tin bisporphyrinates were synthesized. Their absorption spectra have been analyzed in terms of exciton interaction and porphyrin−bridge coupling by through-bond interaction and the steady-state fluorescence spectra in terms of differential Stokes shifts for the electron-donating zinc and the electron-accepting tin porphyrinates. Strong quenching of the fluorescence intensity and acceleration of the fluorescence decay as compared to porphyrinate monomers (ZnTPP, SnTPP) were observed. Both phenomena were traced back to light-induced electron transfer by the occurrence of ion pair absorption bands in picosecond transient absorption spectra. Similar absorption spectra of both chromophores caused always simultaneous excitation and, consequently, two concurrent photoreactions. Combined evaluation of the time-dependent absorption and fluorescence data allowed the estimation of rates for the electron transfer reactions. The found dependence on the separation distance was much smaller than for donor−acceptor systems with saturated spacers. A damping factor of 0.05 was calculated for the charge separation proceeding from the excited state of the zinc porphyrin. The polarity of the solvent had a profound influence on the transfer rates. The charge recombination was 300 times faster in polar tetrahydrofuran than in nonpolar toluene.

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