Temperature-dependent behavior of the dual fluorescence of 2-(3-fluorophenyl)-2,3-dihydro-1H-benzo[f]isoindole-1,3-dione

Pierre Valat, Véronique Wintgens, Jean Kossanyi, L. Biczók, A. Demeter, T. Bérces

Research output: Contribution to journalArticle

11 Citations (Scopus)

Abstract

The fluorescence behavior of 2-(3-fluorophenyl)-2,3-dihydro-1H-benzo[f]isoindole-1,3-dione (1) was studied in solvents of different polarity and viscosity. Dual luminescence is observed and the short-wavelength emission is found to increase considerably with the solvent polarity. The ratio of the fluorescence quantum yield of the two states emitting, the one (SW*) at short wavelength and the other (LW*) at long wavelength, shows a bell-shaped dependence on the reciprocal of the temperature in diethyl ether, butyronitrile, and propane-1,2,3-triol triacetate (glycerol triacetate; GTA). This has been interpreted as the result of a reversible interconversion between the two states. The enthalpy difference between the SW* and LW* excited states, as deduced from the slope of the ln (Φf LWf)SW vs. 1/T curves in the high temperature range, is found to be solvent polarity and solvent viscosity independent as the same value (-7.3 kJ/mol) is obtained in the three above-mentioned solvents. The independence from polarity is the consequence of a similar difference in dipole moment between the ground-state and the SW* and LW* excited states (4.5 and 4.9 D, respectively, derived from solvatochromy). The activation energy of the SW*→LW* step deduced from the low temperature measurements in the nonviscous solvents, increases with solvent polarity (11.6 and 17.5 kJ/mol for diethyl ether and butyronitrile, respectively); they are greater than the viscous-flow activation energy of the solvents indicating that the resolvation of the excited dipole controls the kinetics. In the nonviscous solvents, the LW* state originates from the SW* state, while in the viscous GTA solution, both states are formed simultaneously within the 1-ps laser pulse.

Original languageEnglish
Pages (from-to)2813-2832
Number of pages20
JournalHelvetica Chimica Acta
Volume84
Issue number9
DOIs
Publication statusPublished - 2001

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Isoindoles
Dione
Fluorescence
fluorescence
Temperature
polarity
temperature
diethyl ether
Excited states
Viscosity
Wavelength
Ether
Ethers
Activation energy
triols
wavelengths
viscosity
activation energy
Propane
Dipole moment

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Temperature-dependent behavior of the dual fluorescence of 2-(3-fluorophenyl)-2,3-dihydro-1H-benzo[f]isoindole-1,3-dione. / Valat, Pierre; Wintgens, Véronique; Kossanyi, Jean; Biczók, L.; Demeter, A.; Bérces, T.

In: Helvetica Chimica Acta, Vol. 84, No. 9, 2001, p. 2813-2832.

Research output: Contribution to journalArticle

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abstract = "The fluorescence behavior of 2-(3-fluorophenyl)-2,3-dihydro-1H-benzo[f]isoindole-1,3-dione (1) was studied in solvents of different polarity and viscosity. Dual luminescence is observed and the short-wavelength emission is found to increase considerably with the solvent polarity. The ratio of the fluorescence quantum yield of the two states emitting, the one (SW*) at short wavelength and the other (LW*) at long wavelength, shows a bell-shaped dependence on the reciprocal of the temperature in diethyl ether, butyronitrile, and propane-1,2,3-triol triacetate (glycerol triacetate; GTA). This has been interpreted as the result of a reversible interconversion between the two states. The enthalpy difference between the SW* and LW* excited states, as deduced from the slope of the ln (Φf LW/Φf)SW vs. 1/T curves in the high temperature range, is found to be solvent polarity and solvent viscosity independent as the same value (-7.3 kJ/mol) is obtained in the three above-mentioned solvents. The independence from polarity is the consequence of a similar difference in dipole moment between the ground-state and the SW* and LW* excited states (4.5 and 4.9 D, respectively, derived from solvatochromy). The activation energy of the SW*→LW* step deduced from the low temperature measurements in the nonviscous solvents, increases with solvent polarity (11.6 and 17.5 kJ/mol for diethyl ether and butyronitrile, respectively); they are greater than the viscous-flow activation energy of the solvents indicating that the resolvation of the excited dipole controls the kinetics. In the nonviscous solvents, the LW* state originates from the SW* state, while in the viscous GTA solution, both states are formed simultaneously within the 1-ps laser pulse.",
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AU - Demeter, A.

AU - Bérces, T.

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