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Dipole Effects on Electron Transfer are Enormous
Author(s) -
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.
Publication year - 2018
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201802637
Subject(s) - dipole , chemical physics , polarity (international relations) , electron , orientation (vector space) , electron transfer , chemistry , molecular physics , physics , nanotechnology , atomic physics , materials science , photochemistry , quantum mechanics , geometry , biochemistry , mathematics , cell
Abstract 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.