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

Research output: Contribution to journalArticle

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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

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Porphyrins
porphyrins
electron transfer
zinc
Electrons
Gold
Tin
gold
tin
Fullerenes
solar energy conversion
electrons
Potassium Chloride
rings
dichlorides
Energy conversion
electronics
Discrete Fourier transforms
Solar energy
fullerenes

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Physical and Theoretical Chemistry

Cite this

Göransson, E., Boixel, J., Fortage, J., Jacquemin, D., Becker, H. C., Blart, E., ... 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

Long-range electron transfer in zinc-phthalocyanine-oligo(Phenylene- ethynylene)-based donor-bridge-acceptor dyads. / Göransson, Erik; Boixel, Julien; Fortage, Jérôme; Jacquemin, Denis; Becker, Hans Christian; Blart, Errol; Hammarström, Leif; Odobel, Fabrice.

In: Inorganic Chemistry, Vol. 51, No. 21, 05.11.2012, p. 11500-11512.

Research output: Contribution to journalArticle

Göransson, E, Boixel, J, Fortage, J, Jacquemin, D, Becker, HC, Blart, E, Hammarström, L & Odobel, F 2012, 'Long-range electron transfer in zinc-phthalocyanine-oligo(Phenylene- ethynylene)-based donor-bridge-acceptor dyads', Inorganic Chemistry, vol. 51, no. 21, pp. 11500-11512. https://doi.org/10.1021/ic3013552
Göransson, Erik ; Boixel, Julien ; Fortage, Jérôme ; Jacquemin, Denis ; Becker, Hans Christian ; Blart, Errol ; Hammarström, Leif ; Odobel, Fabrice. / Long-range electron transfer in zinc-phthalocyanine-oligo(Phenylene- ethynylene)-based donor-bridge-acceptor dyads. In: Inorganic Chemistry. 2012 ; Vol. 51, No. 21. pp. 11500-11512.
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