Jump to main content
Jump to site search

Issue 38, 2015
Previous Article Next Article

Hole-transfer induced energy transfer in perylene diimide dyads with a donor–spacer–acceptor motif

Author affiliations

Abstract

We investigate the photoinduced dynamics of perylene diimide dyads based on a donor–spacer–acceptor motif with polyyne spacers of varying length by pump–probe spectroscopy, time resolved fluorescence, chemical variation and quantum chemistry. While the dyads with pyridine based polyyne spacers undergo energy transfer with near-unity quantum efficiency, in the dyads with phenyl based polyyne spacers the energy transfer efficiency drops below 50%. This suggests the presence of a competing electron transfer process from the spacer to the energy donor as the excitation sink. Transient absorption spectra, however, reveal that the spacer actually mediates the energy transfer dynamics. The ground state bleach features of the polyyne spacers appear due to the electron transfer decay with the same time constant present in the rise of the ground state bleach and stimulated emission of the perylene energy acceptor. Although the electron transfer process initially quenches the fluorescence of the donor it does not inhibit energy transfer to the perylene energy acceptor. The transient signatures reveal that electron and energy transfer processes are sequential and indicate that the donor–spacer electron transfer state itself is responsible for the energy transfer. Through the introduction of a Dexter blocker unit into the spacer we can clearly exclude any through bond Dexter-type energy transfer. Ab initio calculations on the donor–spacer and the donor–spacer–acceptor systems reveal the existence of a bright charge transfer state that is close in energy to the locally excited state of the acceptor. Multipole–multipole interactions between the bright charge transfer state and the acceptor state enable the energy transfer. We term this mechanism coupled hole-transfer FRET. These dyads represent a first example that shows how electron transfer can be connected to energy transfer for use in novel photovoltaic and optoelectronic devices.

Graphical abstract: Hole-transfer induced energy transfer in perylene diimide dyads with a donor–spacer–acceptor motif

Back to tab navigation

Supplementary files

Publication details

The article was received on 23 May 2015, accepted on 23 Aug 2015 and first published on 24 Aug 2015


Article type: Paper
DOI: 10.1039/C5CP02981C
Author version
available:
Download author version (PDF)
Citation: Phys. Chem. Chem. Phys., 2015,17, 25061-25072
  • Open access: Creative Commons BY license
  •   Request permissions

    Hole-transfer induced energy transfer in perylene diimide dyads with a donor–spacer–acceptor motif

    P. Kölle, I. Pugliesi, H. Langhals, R. Wilcken, A. J. Esterbauer, R. de Vivie-Riedle and E. Riedle, Phys. Chem. Chem. Phys., 2015, 17, 25061
    DOI: 10.1039/C5CP02981C

    This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. Material from this article can be used in other publications provided that the correct acknowledgement is given with the reproduced material.

    Reproduced material should be attributed as follows:

    • For reproduction of material from NJC:
      [Original citation] - Published by The Royal Society of Chemistry (RSC) on behalf of the Centre National de la Recherche Scientifique (CNRS) and the RSC.
    • For reproduction of material from PCCP:
      [Original citation] - Published by the PCCP Owner Societies.
    • For reproduction of material from PPS:
      [Original citation] - Published by The Royal Society of Chemistry (RSC) on behalf of the European Society for Photobiology, the European Photochemistry Association, and RSC.
    • For reproduction of material from all other RSC journals:
      [Original citation] - Published by The Royal Society of Chemistry.

    Information about reproducing material from RSC articles with different licences is available on our Permission Requests page.

Search articles by author

Spotlight

Advertisements