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Aminorhodamine (ARh): A Bichromophore with Three Emission Bands in Low Temperature Glasses
Thomas Just Sørensen1, Kristine Kilså2,3, Bo W Laursen4
1Nano-Science Center and Department of Chemistry, University of Copenhagen, Universitetsparken 5, 2100 København Ø (Denmark). TJS@chem.ku.dk.
Abstract:
At first glance, aminorhodamine (ARh) is a typical pH responsive fluorescent, rhodamine-type dye. However, hidden under the typical rhodamine absorption band, ARh has another electronic transition of similar energy, but polarized orthogonal to that of the rhodamine chromophore. This transition-assigned to an arylpyrylium type chromophore contained in the system-is responsible for the sensor action of the dye. ARh is non-fluorescent, while protonation of a donor amino group turn on a strong rhodamine-type emission. At low temperature in frozen solution emission from both electronic subsystems of ARh are observed. In order to achieve more complete understanding of the photophysical mechanisms in this type of fluorescent probes, ARh and its protonated counterpart HARh were studied by absorption and fluorescence spectroscopy, computational chemistry, and at low temperatures in solid solution. Results from fluorescence anisotropy and time-resolved fluorescence spectra establish a bichromophore model and suggest that a remarkable weak coupling between the two nearly isoenergetic excited states in ARh enables the dual emission. All the complicated properties observed for ARh was accounted for by a bichromophore model describing the electronic system of ARh as a bichromophore constituted by a rhodamine and an arylpyrylium subsystem.
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