10.1021/jp412129m.s001
Constanza Ruiz
Constanza
Ruiz
Eva M. García-Frutos
Eva M.
García-Frutos
Demetrio A. da
Silva Filho
Demetrio
A. da
Silva Filho
Juan T. López Navarrete
Juan
T. López Navarrete
M. Carmen Ruiz Delgado
M.
Carmen Ruiz Delgado
Berta Gómez-Lor
Berta
Gómez-Lor
Symmetry
Lowering in Triindoles: Impact on the Electronic and Photophysical
Properties
American Chemical Society
2014
Cyclic voltammetry
oxidation processes
cyclic voltammetry
fluorescence enhancement
hole mobility semiconductor
Photophysical PropertiesThe
triindole platform
fluorescence quantum
Symmetry Lowering
symmetry
photophysical properties
cyclic dehydrotrimer
reorganization energies
absorption edge
dihydro
triindole platform causes
alkyl groups
physicochemical properties
spectroelectrochemistry
nitrogen atoms results
emission maxima
DFT calculations
emission spectroscopies
2014-03-13 00:00:00
Journal contribution
https://acs.figshare.com/articles/journal_contribution/Symmetry_Lowering_in_Triindoles_Impact_on_the_Electronic_and_Photophysical_Properties/2314897
The electronic and photophysical
properties of 6,11-dihydro-5<i>H</i>-diindolo[2,3-<i>a</i>:2′,3′-<i>c</i>]carbazole, an asymmetric
cyclic dehydrotrimer of indole, have been explored and compared to
its symmetric analogue, 10,15-dihydro-5<i>H</i>-diindolo[3,2-<i>a</i>:3′,2′-<i>c</i>]carbazole (triindole),
a well-known high hole mobility semiconductor. To this purpose, we
use a joint experimental and theoretical approach that combines absorption
and emission spectroscopies, cyclic voltammetry, and spectroelectrochemistry
with DFT calculations. Lowering the symmetry of the triindole platform
causes a red-shift of the absorption edge and emission maxima and
improved the fluorescence quantum yield. Cyclic voltammetry and spectroelectrochemistry
reveal the reversible nature of the two observable oxidation processes
in the alkylated asymmetric triindoles together with an increase in
the stabillity of their oxidized species. On the other hand, the insertion
of alkyl groups on the nitrogen atoms results in a further fluorescence
enhancement although larger reorganization energies are found. DFT
and time-dependent (TD-DFT) calculations successfully support the
experimental data and aid in the understanding of the tuning of the
physicochemical properties of the triindole platform upon symmetry
lowering toward their incorporation in electronic devices.