Journal
JOURNAL OF FLUORESCENCE
Volume 16, Issue 1, Pages 77-86Publisher
SPRINGER/PLENUM PUBLISHERS
DOI: 10.1007/s10895-005-0053-9
Keywords
fluorosolvatochromism; preferential solvation; solvatochromic dyes; binary mixtures; merocyanines
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The fluorescence-based solvatochromism (fluorosolvatochromism) of 4-[(1-methyl-4(1H)pyridinylidene)- ethylidene]- 2,5-cyclohexadien-1-one (Brooker's merocyanine) was studied. The results revealed that the fluorescence emission band of the dye was dependent on the medium (lambda(fl)(max) = 573 nm in water and lambda(fl)(max) = 622 nm in DMF). The fluorescence quantum yields (phi(f)) were calculated for the dye in the solvents investigated. Low phi(f) values ( < 10%) were obtained for the dye and in order to better comprehend the radiative and nonradiative decay processes of this dye, its fluorescence lifetime in methanol was measured and was found to be very short ( 230 ps). The results suggest that the dye in the excited state decays rapidly through nonradiative processes. The behavior of the probe in binary mixtures including a hydrogen-bond accepting solvent ( acetonitrile, N,N-dimethylformamide, and dimethylsulfoxide) and a hydroxylic solvent ( water, methanol, ethanol, propan-2-ol, and butan-1-ol) was also investigated. All data were successfully fitted to a model based on solvent exchange equilibria, which allowed the separation of the different contributions of the solvent species in the solvation shell of the dye. The data obtained for the mixed solvents were explained based on solute - solvent and solvent - solvent interactions.
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