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On the Observation of Intervalence Charge Transfer Bands in Hydrogen-Bonded Mixed-Valence Complexes.
- Source :
-
Journal of the American Chemical Society . 2/5/2014, Vol. 136 Issue 5, p1710-1713. 4p. - Publication Year :
- 2014
-
Abstract
- Ruthenium clusters of the type [Ru3(μ3-O)(OAc)6(CO)(L)(nic)], where L = 4-dimethylaminopyridine (dmap) and nic = isonicotinic acid, form hydrogen-bonded mixed-valence dimers upon a single electron reduction. Electrochemical responses show two overlapping reduction waves, indicating the presence of a thermodynamically stable mixed-valence dimer with considerable electronic coupling across the hydrogen bond. Electronic spectra of the singly reduced hydrogen-bonded mixed-valence dimer reveal two intervalence charge transfer bands in the near-infrared region consistent with a Robin-Day class II system. These bands are assigned as metal-to-metal and metal-to-bridge charge transfer, and their behavior is best described by a semiclassical three state model. Infrared spectroscopy suggests localized behavior indicating electron transfer between the two clusters is slower than 1010 s–1. [ABSTRACT FROM AUTHOR]
Details
- Language :
- English
- ISSN :
- 00027863
- Volume :
- 136
- Issue :
- 5
- Database :
- Academic Search Index
- Journal :
- Journal of the American Chemical Society
- Publication Type :
- Academic Journal
- Accession number :
- 95061621
- Full Text :
- https://doi.org/10.1021/ja410540m