Long-range electron transfer in zinc-phthalocyanine-oligo(Phenylene- ethynylene)-based donor-bridge-acceptor dyads

Erik Göransson, Julien Boixel, Jérôme Fortage, Denis Jacquemin, Hans Christian Becker, Errol Blart, Leif Hammarström, Fabrice Odobel

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Abstract

In the context of long-range electron transfer for solar energy conversion, we present the synthesis, photophysical, and computational characterization of two new zinc(II) phthalocyanine oligophenylene-ethynylene based donor-bride-acceptor dyads: ZnPc-OPE-AuP+ and ZnPc-OPE-C 60. A gold(III) porphyrin and a fullerene has been used as electron accepting moieties, and the results have been compared to a previously reported dyad with a tin(IV) dichloride porphyrin as the electron acceptor (Fortage et al. Chem. Commun.2007, 4629). The results for ZnPc-OPE-AuP+ indicate a remarkably strong electronic coupling over a distance of more than 3 nm. The electronic coupling is manifested in both the absorption spectrum and an ultrafast rate for photoinduced electron transfer (kPET = 1.0 × 1012 s-1). The charge-shifted state in ZnPc-OPE-AuP + recombines with a relatively low rate (kBET = 1.0 × 109 s-1). In contrast, the rate for charge transfer in the other dyad, ZnPc-OPE-C60, is relatively slow (k PET = 1.1 × 109 s-1), while the recombination is very fast (kBET ≈ 5 × 1010 s-1). TD-DFT calculations support the hypothesis that the long-lived charge-shifted state of ZnPc-OPE-AuP+ is due to relaxation of the reduced gold porphyrin from a porphyrin ring based reduction to a gold centered reduction. This is in contrast to the faster recombination in the tin(IV) porphyrin based system (kBET = 1.2 × 1010 s -1), where the excess electron is instead delocalized over the porphyrin ring.

Original languageEnglish
Pages (from-to)11500-11512
Number of pages13
JournalInorganic Chemistry
Volume51
Issue number21
DOIs
Publication statusPublished - Nov 5 2012

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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    Göransson, E., Boixel, J., Fortage, J., Jacquemin, D., Becker, H. C., Blart, E., Hammarström, L., & Odobel, F. (2012). Long-range electron transfer in zinc-phthalocyanine-oligo(Phenylene- ethynylene)-based donor-bridge-acceptor dyads. Inorganic Chemistry, 51(21), 11500-11512. https://doi.org/10.1021/ic3013552