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Issue 38, 2015
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Hole-transfer induced energy transfer in perylene diimide dyads with a donor–spacer–acceptor motif

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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

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Supplementary files

Article information


Submitted
23 May 2015
Accepted
23 Aug 2015
First published
24 Aug 2015

This article is Open Access

Phys. Chem. Chem. Phys., 2015,17, 25061-25072
Article type
Paper
Author version available

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

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