Fluorescence quenching of aromatic hydrocarbons by nitroxide radicals: a mechanismatic study

The fluorescence quenching of phenanthrene (Phen), 9-cyanophenanthrene (CPhen), 9-cyanoanthracene (CA), perylene (Per), 9,10-dicyanoanthracene (DCA), and 9,10-diphenylanthracene (DPA) using stable nitroxide radicals as quenchers has been studied by steady state and flash photolysis measurements. Bot...

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Main Authors: Tarek A. Fayed, Gunter Grampp, Stephan Landgraf
Format: Article
Language:English
Published: Wiley 1999-01-01
Series:International Journal of Photoenergy
Online Access:http://dx.doi.org/10.1155/S1110662X99000306
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author Tarek A. Fayed
Gunter Grampp
Stephan Landgraf
author_facet Tarek A. Fayed
Gunter Grampp
Stephan Landgraf
author_sort Tarek A. Fayed
collection DOAJ
description The fluorescence quenching of phenanthrene (Phen), 9-cyanophenanthrene (CPhen), 9-cyanoanthracene (CA), perylene (Per), 9,10-dicyanoanthracene (DCA), and 9,10-diphenylanthracene (DPA) using stable nitroxide radicals as quenchers has been studied by steady state and flash photolysis measurements. Both linearity and deviation from linearity in the Stern-Volmer plots have been observed. The active sphere model was used to discuss the upward curvature of the Stern-Volmer plots in case of Per, DCA, and DPA. The bimolecular quenching rate constant (kq) of Phen, CPhen and CA was found to be diffusion controlled while in other cases it is lower than the diffusion limit. On the basis of flash photolysis measurements as well as the overlap between the emission spectra of hydrocarbons and the absorption spectra of radicals, a resonance energy transfer mechanism is taken place in case of Per, DPA, DCA, and CA. For Phen and CPhen where the energy gap between the first excited singlet and the nearest lower triplet state is small, an induced intersystem crossing was suggested. Finally, the quenching process was discussed in terms of the free energy dependence (ΔG) of the electron transfer from nitroxide radicals to the excited hydrocarbons.
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spelling doaj-art-4292f4253b0f4bf9b703e0d0928d7e212025-08-20T02:39:15ZengWileyInternational Journal of Photoenergy1110-662X1999-01-011317317610.1155/S1110662X99000306Fluorescence quenching of aromatic hydrocarbons by nitroxide radicals: a mechanismatic studyTarek A. Fayed0Gunter Grampp1Stephan Landgraf2Institute of Physical and Theoretical Chemistry, Technical University Graz, Technikerstr 4/I, Graz 8010, AustriaInstitute of Physical and Theoretical Chemistry, Technical University Graz, Technikerstr 4/I, Graz 8010, AustriaInstitute of Physical and Theoretical Chemistry, Technical University Graz, Technikerstr 4/I, Graz 8010, AustriaThe fluorescence quenching of phenanthrene (Phen), 9-cyanophenanthrene (CPhen), 9-cyanoanthracene (CA), perylene (Per), 9,10-dicyanoanthracene (DCA), and 9,10-diphenylanthracene (DPA) using stable nitroxide radicals as quenchers has been studied by steady state and flash photolysis measurements. Both linearity and deviation from linearity in the Stern-Volmer plots have been observed. The active sphere model was used to discuss the upward curvature of the Stern-Volmer plots in case of Per, DCA, and DPA. The bimolecular quenching rate constant (kq) of Phen, CPhen and CA was found to be diffusion controlled while in other cases it is lower than the diffusion limit. On the basis of flash photolysis measurements as well as the overlap between the emission spectra of hydrocarbons and the absorption spectra of radicals, a resonance energy transfer mechanism is taken place in case of Per, DPA, DCA, and CA. For Phen and CPhen where the energy gap between the first excited singlet and the nearest lower triplet state is small, an induced intersystem crossing was suggested. Finally, the quenching process was discussed in terms of the free energy dependence (ΔG) of the electron transfer from nitroxide radicals to the excited hydrocarbons.http://dx.doi.org/10.1155/S1110662X99000306
spellingShingle Tarek A. Fayed
Gunter Grampp
Stephan Landgraf
Fluorescence quenching of aromatic hydrocarbons by nitroxide radicals: a mechanismatic study
International Journal of Photoenergy
title Fluorescence quenching of aromatic hydrocarbons by nitroxide radicals: a mechanismatic study
title_full Fluorescence quenching of aromatic hydrocarbons by nitroxide radicals: a mechanismatic study
title_fullStr Fluorescence quenching of aromatic hydrocarbons by nitroxide radicals: a mechanismatic study
title_full_unstemmed Fluorescence quenching of aromatic hydrocarbons by nitroxide radicals: a mechanismatic study
title_short Fluorescence quenching of aromatic hydrocarbons by nitroxide radicals: a mechanismatic study
title_sort fluorescence quenching of aromatic hydrocarbons by nitroxide radicals a mechanismatic study
url http://dx.doi.org/10.1155/S1110662X99000306
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AT guntergrampp fluorescencequenchingofaromatichydrocarbonsbynitroxideradicalsamechanismaticstudy
AT stephanlandgraf fluorescencequenchingofaromatichydrocarbonsbynitroxideradicalsamechanismaticstudy