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Ultrafast Voltammetry for Probing Interfacial Electron Transfer in Molecular Wires
Author(s) -
Amatore Christian,
Maisonhaute Emmanuel,
Schöllhorn Bernd,
Wadhawan Jay
Publication year - 2007
Publication title -
chemphyschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.016
H-Index - 140
eISSN - 1439-7641
pISSN - 1439-4235
DOI - 10.1002/cphc.200600774
Subject(s) - counterion , electron transfer , chemistry , cyclic voltammetry , superexchange , redox , monolayer , chemical physics , reaction rate constant , photochemistry , electrolyte , voltammetry , inorganic chemistry , electrochemistry , ion , electrode , organic chemistry , kinetics , biochemistry , physics , quantum mechanics
Electron transfer inside self‐assembled monolayers made from complex redox‐active oligophenylenevinylene molecular wires is examined by ultrafast cyclic voltammetry. Rate constants above 10 6 s −1 are measured when the electroactive moieties are easily accessible to counterions from the electrolyte. These counterion movements are necessary to compensate the local charge created upon electron transfer. Conversely, if the redox center is buried within long hydrophobic diluents, the counterion movement towards the redox entity becomes rate limiting, thus drastically altering the rate magnitude and its physical meaning. This change in the mechanism is examined both for superexchange or when one electron‐hopping step is involved.