TY - JOUR
T1 - Time-resolved electron transfer in porphyrin-coordinated ruthenium dimers
T2 - From mixed-valence dynamics to hot electron transfer
AU - Petersson, Jonas
AU - Henderson, Jane
AU - Brown, Allison
AU - Hammarström, Leif
AU - Kubiak, Clifford P.
N1 - Publisher Copyright:
© 2015 American Chemical Society.
Copyright:
Copyright 2015 Elsevier B.V., All rights reserved.
PY - 2015/3/5
Y1 - 2015/3/5
N2 - Presented here is the first effort to study the formation and dynamics of the triruthenium cluster (Ru3O) pyrazine-bridged dimer mixed-valence state. Femtosecond transient absorption spectroscopy was implemented to follow photoinduced electron-transfer reactions in a series of asymmetric porphyrin-coordinated dyads, which form strongly coupled mixed-valence species upon single reduction. Excitation of the porphyrin subunit resulted in electron transfer to the Ru3O dimer with a time constant τ ≈ 0.6 ps. The intramolecular electron transfer was confirmed by excitation of the Ru3O MLCT, which resulted in the formation of a vibrationally unrelaxed porphyrin ground state. Under both excitation experiments, the back electron transfer was extremely fast (τCR < 0.1 ps), preventing complete time-resolved exploration of the mixed-valence state. These complexes enabled the observation of excited product states following electron-transfer processes, resulting from porphyrin S1 and S2 excitation. Although the charge recombination itself could not be observed, the yield of unrelaxed ground states supports the conclusion that delocalization takes place at least partially on a sub-100 fs time scale.
AB - Presented here is the first effort to study the formation and dynamics of the triruthenium cluster (Ru3O) pyrazine-bridged dimer mixed-valence state. Femtosecond transient absorption spectroscopy was implemented to follow photoinduced electron-transfer reactions in a series of asymmetric porphyrin-coordinated dyads, which form strongly coupled mixed-valence species upon single reduction. Excitation of the porphyrin subunit resulted in electron transfer to the Ru3O dimer with a time constant τ ≈ 0.6 ps. The intramolecular electron transfer was confirmed by excitation of the Ru3O MLCT, which resulted in the formation of a vibrationally unrelaxed porphyrin ground state. Under both excitation experiments, the back electron transfer was extremely fast (τCR < 0.1 ps), preventing complete time-resolved exploration of the mixed-valence state. These complexes enabled the observation of excited product states following electron-transfer processes, resulting from porphyrin S1 and S2 excitation. Although the charge recombination itself could not be observed, the yield of unrelaxed ground states supports the conclusion that delocalization takes place at least partially on a sub-100 fs time scale.
UR - http://www.scopus.com/inward/record.url?scp=84924169559&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=84924169559&partnerID=8YFLogxK
U2 - 10.1021/jp510782c
DO - 10.1021/jp510782c
M3 - Article
AN - SCOPUS:84924169559
VL - 119
SP - 4479
EP - 4487
JO - Journal of Physical Chemistry C
JF - Journal of Physical Chemistry C
SN - 1932-7447
IS - 9
ER -