TY - JOUR
T1 - Trends in electron-vibration and electronic interactions in bis(dimethylamino) mixed-valence systems
T2 - A joint experimental and theoretical investigation
AU - Risko, Chad
AU - Coropceanu, Veaceslav
AU - Barlow, Stephen
AU - Geskin, Victor
AU - Schmidt, Karin
AU - Gruhn, Nadine E.
AU - Marder, Seth R.
AU - Bredas, Jean Luc
PY - 2008/5/29
Y1 - 2008/5/29
N2 - By using gas-phase ultraviolet photoelectron spectroscopy, vis/NIR spectroscopy, and electronic-structure calculations, we have investigated the electron-vibration and electronic interactions in a series of bisdimethylamino mixed-valence systems: N,N,N′,N′-tetramethyl-p-phenylenediamine, N,N,N′,N′-tetramethylbenzidine, and N,N,N′,N′- tetramethyltolane-4,4′-diamine. Experiment and theory concur to indicate that the electron-vibration coupling in these systems is dominated by interactions with symmetric modes. The results reveal that the strength of both electronic and electron-vibration couplings decreases as the molecular bridge lengthens. The parameters derived for the present compounds have been compared to those of diarylaminobased structural analogs. This comparison underlines that the replacement of the methyl terminal groups with p-anisyl groups has a significant effect on the electronic and electron-vibrational interactions.
AB - By using gas-phase ultraviolet photoelectron spectroscopy, vis/NIR spectroscopy, and electronic-structure calculations, we have investigated the electron-vibration and electronic interactions in a series of bisdimethylamino mixed-valence systems: N,N,N′,N′-tetramethyl-p-phenylenediamine, N,N,N′,N′-tetramethylbenzidine, and N,N,N′,N′- tetramethyltolane-4,4′-diamine. Experiment and theory concur to indicate that the electron-vibration coupling in these systems is dominated by interactions with symmetric modes. The results reveal that the strength of both electronic and electron-vibration couplings decreases as the molecular bridge lengthens. The parameters derived for the present compounds have been compared to those of diarylaminobased structural analogs. This comparison underlines that the replacement of the methyl terminal groups with p-anisyl groups has a significant effect on the electronic and electron-vibrational interactions.
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U2 - 10.1021/jp711954j
DO - 10.1021/jp711954j
M3 - Article
AN - SCOPUS:53349163433
SN - 1932-7447
VL - 112
SP - 7959
EP - 7967
JO - Journal of Physical Chemistry C
JF - Journal of Physical Chemistry C
IS - 21
ER -