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. 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 ( k q ) 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 ( Δ G ) of the electron transfer from nitroxide radicals to the excited hydrocarbons.