UNIGE document Scientific Article
previous document  unige:3275  next document
add to browser collection
Title

Time-Resolved Spectroscopy of the Metal-to-Metal Charge Transfer Excited State in Dinuclear Cyano-Bridged Mixed-Valence Complexes

Authors
Macpherson, Brendan P.
Bernhardt, Paul V.
Published in Inorganic Chemistry. 2005, vol. 44, no. 15, p. 5530-5536
Abstract Visible pump−probe spectroscopy has been used to identify and characterize short-lived metal-to-metal charge transfer (MMCT) excited states in a group of cyano-bridged mixed-valence complexes of the formula [LCoIIINCMII(CN)5]-, where L is a pentadentate macrocyclic pentaamine (L14) or triamine-dithiaether (L14S) and M is Fe or Ru. Nanosecond pump−probe spectroscopy on frozen solutions of [L14CoIIINCFeII(CN)5]- and [L14SCoIIINCFeII(CN)5]- at 11 K enabled the construction of difference transient absorption spectra that featured a rise in absorbance in the region of 350−400 nm consistent with the generation of the ferricyanide chromophore of the photoexcited complex. The MMCT excited state of the Ru analogue [L14CoIIINCRuII(CN)5]- was too short-lived to allow its detection. Femtosecond pump−probe spectroscopy on aqueous solutions of [L14CoIIINCFeII(CN)5]- and [L14SCoIIINCFeII(CN)5]- at room temperature enabled the lifetimes of their CoII−FeIII MMCT excited states to be determined as 0.8 and 1.3 ps, respectively.
Identifiers
Full text
Structures
Research groups Groupe Hauser
Groupe Vauthey
Citation
(ISO format)
MACPHERSON, Brendan P. et al. Time-Resolved Spectroscopy of the Metal-to-Metal Charge Transfer Excited State in Dinuclear Cyano-Bridged Mixed-Valence Complexes. In: Inorganic Chemistry, 2005, vol. 44, n° 15, p. 5530-5536. https://archive-ouverte.unige.ch/unige:3275

225 hits

127 downloads

Update

Deposited on : 2009-09-21

Export document
Format :
Citation style :