TY - JOUR
T1 - Excited State Mixed-Valence Complexes
T2 - From the Special Pair to the Creutz–Taube Ion and Beyond
AU - Low, Paul J.
PY - 2023/4
Y1 - 2023/4
N2 - Compounds and complexes with mixed-valence electronic ground states, such as the Creutz–Taube ion, have proven to be excellent vehicles through which to study intramolecular electron-transfer processes. In a recent contribution by Cadranel and co-workers, time-resolved pump-probe spectroscopy reveals photo-induced metal-to-bridge charge transfer within the homovalent analogue of the Creutz–Taube ion, [{(NH3)5Ru}(μ-pz){Ru(NH3)5}]4+, giving rise to two closely lying excited states with mixed-valence character, one with a shorter lifetime (τ=136 ps) and weakly-coupled (Robin-Day Class II) character, the other a longer-lived (τ=2.8 ns) configurational isomer with more delocalized electronic structure. Electron transfer reactions from the longer-lived species demonstrate analogies with the photo-induced reactions of the photosynthetic special pair, suggesting this state as a reference system for excited state mixed-valency, and a framework from which to explore photocatalytic reactions.
AB - Compounds and complexes with mixed-valence electronic ground states, such as the Creutz–Taube ion, have proven to be excellent vehicles through which to study intramolecular electron-transfer processes. In a recent contribution by Cadranel and co-workers, time-resolved pump-probe spectroscopy reveals photo-induced metal-to-bridge charge transfer within the homovalent analogue of the Creutz–Taube ion, [{(NH3)5Ru}(μ-pz){Ru(NH3)5}]4+, giving rise to two closely lying excited states with mixed-valence character, one with a shorter lifetime (τ=136 ps) and weakly-coupled (Robin-Day Class II) character, the other a longer-lived (τ=2.8 ns) configurational isomer with more delocalized electronic structure. Electron transfer reactions from the longer-lived species demonstrate analogies with the photo-induced reactions of the photosynthetic special pair, suggesting this state as a reference system for excited state mixed-valency, and a framework from which to explore photocatalytic reactions.
KW - Electron Transfer
KW - Excited States
KW - Mixed-Valence
KW - Photosynthesis
KW - Time-Resolved Spectroscopy
UR - http://www.scopus.com/inward/record.url?scp=85147574310&partnerID=8YFLogxK
U2 - 10.1002/anie.202217082
DO - 10.1002/anie.202217082
M3 - Article
C2 - 36691301
AN - SCOPUS:85147574310
SN - 1433-7851
VL - 62
JO - Angewandte Chemie - International Edition
JF - Angewandte Chemie - International Edition
IS - 15
M1 - e202217082
ER -