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Issue 6, 2013
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Ultrafast photoinduced dynamics of the 3,6-diaminoacridinium derivative ATTO 465 in solution

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Abstract

The excited state dynamics of the dye ATTO 465, a well-known fluorescence marker for biological applications, have been characterized in various solvents including THF, ethanol, methanol, water and the highly polar protic ionic liquid 2-hydroxyethylammonium formate (2-OH-EAF) by combining results from time-correlated single-photon counting (TCSPC) and ultrafast pump–supercontinuum probe (PSCP) spectroscopy as well as steady-state absorption and fluorescence. In water, 2-OH-EAF and two fluorinated alcohols, there is a pronounced blue-shift and broadening of the S0 → S1 absorption band and also a larger Stokes shift than in the other solvents, indicating a particular influence of hydrogen-bonding interactions. S1 lifetimes from TCSPC at 25 °C range from 3.3 ns to 5.6 ns. An unusual increase in the S1 lifetime with temperature is observed for ethanol and methanol, however water behaves in the opposite way. The behavior can be tentatively explained by a solvent- and temperature-dependent “proximity effect”, where coupling of the close-lying S1 and S2 states influences the intramolecular relaxation rate of the dye. In addition, temperature-dependent complex equilibria of ATTO 465 with solvent molecules may influence the measured lifetimes. Several excited-state absorption (ESA) transitions are identified in the PSCP spectra, which are in good agreement with the position of the UV bands in the steady-state absorption spectra. Small shifts of the stimulated emission and ESA bands are consistent with solvation dynamics in the excited electronic state. An additional ∼16 ps component in water, visible over the entire spectral range, is tentatively ascribed to a fast IC channel which is accessed by a fraction of ATTO 465 molecules.

Graphical abstract: Ultrafast photoinduced dynamics of the 3,6-diaminoacridinium derivative ATTO 465 in solution

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Supplementary files

Article information


Submitted
03 Oct 2012
Accepted
28 Nov 2012
First published
18 Dec 2012

Phys. Chem. Chem. Phys., 2013,15, 1844-1853
Article type
Paper

Ultrafast photoinduced dynamics of the 3,6-diaminoacridinium derivative ATTO 465 in solution

J. Arden-Jacob, K. Drexhage, S. I. Druzhinin, M. Ekimova, O. Flender, T. Lenzer, K. Oum and M. Scholz, Phys. Chem. Chem. Phys., 2013, 15, 1844
DOI: 10.1039/C2CP43493H

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