Title: Non-conjugated, phenyl assisted coupling in through bond electron transfer in a perylenemonoimide-triphenylamine system
Authors: Bell, Toby ×
Stefan, Alina
Lemaur, Vincent
Bernhardt, Stefan
Muellen, Klaus
Cornil, Jerome
Beljonne, David
Hofkens, Johan
Van der Auweraer, Mark
De Schryver, Frans #
Issue Date: 2007
Publisher: Royal Society of Chemistry
Series Title: Photochemical & Photobiological Sciences vol:6 issue:4 pages:406-415
Abstract: Two donor-bridge-acceptor compounds containing triphenylamine (TPA) donors and perylenemonoimide (PMI) acceptors have been studied by spectroscopic techniques and quantum chemical computation. Both systems have been observed to emit prompt and delayed fluorescence under certain conditions indicating that forward and reverse electron transfer (ET) processes can occur between the locally excited and the charge separated states. The experimental and computational results show that the TPA and PMI chromophores are better coupled by almost 50% in the meta isomers which undergo ET more readily than the para isomers. Quantum chemical calculations indicate that this unexpected situation is the result of a phenyl group on the side of the bridge being advantageously positioned in the meta isomers. This leads to more extensive delocalisation of the TPA HOMO into the bridge enhancing the total through bond electronic coupling between the TPA and PMI chromophores. The calculations also indicate a strong angle dependence of the total coupling in both isomers. The experimental results are discussed in the context of the high temperature limit of Marcus's theory of non-adiabatic ET.
ISSN: 1474-905X
Publication status: published
KU Leuven publication type: IT
Appears in Collections:Molecular Imaging and Photonics
Chemistry - miscellaneous
× corresponding author
# (joint) last author

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