Publication Type |
Journal Article |
Title |
Electronic Communication in Linear Oligo(azobenzene) Radical Anions |
Authors |
Alvaro Moneo Gonçalo C. Justino M Fernanda NN Carvalho M. Conceição Oliveira Alexandra Maria Moita Antunes David Bleger Stefan Hecht J. P. Telo |
Groups |
BioMol |
Journal |
JOURNAL OF PHYSICAL CHEMISTRY A |
Year |
2013 |
Month |
December |
Volume |
117 |
Number |
51 |
Pages |
14056-14064 |
Abstract |
The radical anions of five bis(azobenzene) and one tris(azobenzene) compounds were studied by optical and electron paramagnetic resonance (EPR) spectroscopies in polar aprotic solvents. The radicals with planar or almost-planar bridges are charge-delocalized mixed-valence species. Localization of charge occurs only on radicals with highly twisted biphenyl bridges. The electronic coupling between the azobenzene charge-bearing units, calculated as half the energy of the intervalence band for the charge-delocalized and by the Hush equation for the charge-localized radicals, decreases with the distance and torsion angle between azobenzene units. These radicals have smaller electronic couplings between charge-bearing units than other mixed-valence organic radicals with similar bridges. However, the application of a three-stage model to the tris(azobenzene) radical anion intervalence band yields an electronic coupling between consecutive azobenzenes that is higher than in any of the bis(azobenzene) radicals studied. |
DOI |
http://dx.doi.org/10.1021/jp407099c |
ISBN |
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Publisher |
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Book Title |
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ISSN |
1089-5639 |
EISSN |
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Conference Name |
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Bibtex ID |
ISI:000329331700014 |
Observations |
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