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On the Coherent Description of Diffusion‐Influenced Fluorescence Quenching Experiments
Author(s) -
Rosspeintner Arnulf,
Kattnig Daniel R.,
Angulo Gonzalo,
Landgraf Stephan,
Grampp Günter,
Cuetos Alejandro
Publication year - 2007
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.200700106
Subject(s) - quenching (fluorescence) , nitrobenzene , electron transfer , diffusion , fluorophore , chemistry , fluorescence , thermodynamics , photochemistry , marcus theory , chemical physics , kinetics , physics , reaction rate constant , organic chemistry , optics , quantum mechanics , catalysis
The fluorescence quenching by electron transfer of a fluorophore, 2,5‐bis(dimethylamino)‐1,3‐benzenedicarbonitrile, to 1,3‐dimethyl‐2‐nitrobenzene, has been studied by means of time‐resolved and steady‐state experiments at different viscosities and up to large quencher concentrations. Differential Encounter Theory (DET) has been used to rationalize the results, in combination with electron transfer modelled by the Marcus theory. Additionally, the solvent structure and the hydrodynamic effect on the diffusion coefficient have been taken into account. Any simpler model failed to simultaneously fit all the results. The large number of quencher concentrations used is crucial to unambiguously extract the electron transfer parameters.