title: Pressure dependence of the dual luminescence of twisting molecules. The case of substituted 2,3-naphthalimides.
abstract: The effect of high pressure (up to 5 kbar) has been studied for triacetin solutions of 2-phenyl-2,3-dihydro-1H-benzo[f]isoindole-1,3dione 1 (N-phenyl-2,3-naphthalimide) and its 3-fluorophenyl- (2), 4-carbethoxyphenyl(4) and 4-methoxyphenyl (5) derivatives which all show dual fluorescence. When the N-phenyl group is unsubstituted (compound 1) or substituted with electron-attracting groups (2 and 4), the increase of pressure over the solution decreases slightly the emission at the long-wavelengths (LW) and increases dramatically the intensity of the short-wavelength (SW) fluorescence. Plotting the logarithm of the SW/LW fluorescence quantum yield ratio for compounds, 1,2 and 4 versus the logarithm of the viscosity of the medium shows a substantial increase of this ratio which corresponds mainly to the increase of the SW emission intensity, the effect on the LW emission being only moderate. As the pressure is increased, the rotation of the N-phenyl group of compound 1 is progressively hindered and the prevailing emission comes from a state which has the same geometry as the ground state (in which the planes of the two moieties of the molecule form an angle close to 60 degree). The effect is different when an electron-donating methoxy group is attached in the para position to the N-phenyl ring, compound 5, as mainly the LW fluorescence intensity increases with pressure. For this molecule which has an electron-donating p-substituent on the N-phenyl ring, the two moieties of the ground state molecule have a more planar geometry (43 degree angle) and the LW fluorescence appears to originate from an intramolecular charge transfer state the fluorescence of which increases with pressure. A three-level reaction scheme is proposed to account for the observed kinetics. In all cases, the viscosity of the medium is found to be the main factor which induces the changes in the fluorescence spectra, and the deceleration of the non-radiative deactivation from the SW* excited state is responsible for these modifications whether a reversible process between the two emitting SW* and LW* states is observed (as for compounds 2 and 4) or not (as for compound 1).
authors.affiliation: Laboratoire de Recherche sur les Polymeres, C.N.R.S., 2-8 rue Henri Dunant, 94320 - Thiais, France. kossanyi@glvt-cnrs.fr
authors.forename: Gaston Hui Bon
authors.initials: GH
authors.lastname: Hoa
authors.forename: Jean
authors.initials: J
authors.lastname: Kossanyi
authors.forename: Attila
authors.initials: A
authors.lastname: Demeter
authors.forename: László
authors.initials: L
authors.lastname: Biczók
authors.forename: Tibor
authors.initials: T
authors.lastname: Bérces