Dipole Effects on Electron Transfer are Enormous

Molecular dipoles present important, but underutilized, methods for guiding electron transfer (ET) processes. While dipoles generate fields of Gigavolts per meter in their vicinity, reported differences between rates of ET along versus against dipoles are often small or undetectable. Herein we show...

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Bibliographic Details
Published in:Angewandte Chemie 2018-09, Vol.130 (38), p.12545-12549
Main Authors: Krzeszewski, Maciej, Espinoza, Eli M., Červinka, Ctirad, Derr, James B., Clark, John A., Borchardt, Dan, Beran, Gregory J. O., Gryko, Daniel T., Vullev, Valentine I.
Format: Article
Language:English
Subjects:
Chemistry
Dipole
Dipoles
Electron transfer
Electrons
Elektronentransfer
Ladungstransfer
Lipophilic
Polarity
Reaktionskinetik
Rehm-Weller-Gleichung
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Summary:Molecular dipoles present important, but underutilized, methods for guiding electron transfer (ET) processes. While dipoles generate fields of Gigavolts per meter in their vicinity, reported differences between rates of ET along versus against dipoles are often small or undetectable. Herein we show unprecedentedly large dipole effects on ET. Depending on their orientation, dipoles either ensure picosecond ET, or turn ET completely off. Furthermore, favorable dipole orientation makes ET possible even in lipophilic medium, which appears counterintuitive for non‐charged donor–acceptor systems. Our analysis reveals that dipoles can substantially alter the ET driving force for low solvent polarity, which accounts for these unique trends. This discovery opens doors for guiding forward ET processes while suppressing undesired backward electron transduction, which is one of the holy grails of photophysics and energy science. Der elektrische Dipol eines Donors beeinflusst den Elektronentransfer (ET) zu einem photochemisch angeregten Akzeptor beträchtlich. In einem weniger polaren Medium wird der Elektronentransfer entlang des Dipols beschleunigt und in die Gegenrichtung komplett unterdrückt. Bei günstiger Dipolausrichtung gelingen Elektronentransfers auch in lipophilem Medium, was für ungeladene Donor‐Akzeptor‐Systeme nicht zu erwarten war.
ISSN:0044-8249
1521-3757
DOI:10.1002/ange.201802637