Preferential solvation of Brooker’s merocyanine in binary solvent mixtures composed of formamides and hydroxylic solvents

Abstract

The E T polarity values of 4-[(1-methyl-4(1 H)-pyridinylidene)-ethylidene]-2,5-cyclohexadien-1-one (Brooker’s merocyanine) were collected in mixed-solvent systems comprising a formamide [ N, N-dimethylformamide (DMF), N-methylformamide (NMF) or formamide (FA)] and a hydroxylic (water, methanol, ethanol, propan-2-ol or butan-1-ol) solvent. Binary mixtures involving DMF and the other formamides (NMF and FA) as well as NMF and FA were also studied. These data were employed in the investigation of the preferential solvation (PS) of the probe. Each solvent system was analyzed in terms of both solute–solvent and solvent–solvent interactions. These latter interactions were responsible for the synergism observed in many binary mixtures. This synergistic behaviour was observed for DMF–propan-2-ol, DMF–butan-1-ol, FA–methanol, FA–ethanol and for the mixtures of the alcohols with NMF. 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 results suggest that both hydrogen bonding and solvophobic interactions contribute to the formation of the solvent complexes responsible for the observed synergistic effects in the PS of the dye.