Specific Solvation of a 4-DASPI Dye in a Water–Ethylene Glycol Binary Solvent

The solvatochromic shifts of the maxima of the absorption spectra of a 4-DASPI dye (4-[4-(dimethylamino)styryl]-1-methylpyridinium iodide) in a water–ethylene glycol binary solvent in a range of concentrations of 0–100% are experimentally studied. The dependence of the solvatochromic shift on the macroscopic permittivity (dielectric constant) of the solution and concentration of ethylene glycol is constructed. The Onsager–Liptay model is applied for the theoretical interpretation which makes it possible to estimate the effective permittivity in the microscopic region directly adjacent to the chromophore based on the values of the measured solvatochromic shifts. It is found that the value of the permittivity in the solvate shell of this dye substantially differs from the macroscopic value of this quantity, which means that the shell is significantly enriched with ethylene glycol (specific solvation) throughout the entire range of concentrations, and the enrichment reaches a maximum approximately in the middle of the specified range. The composition of the solvate shell of the dye at different values of the concentration is discussed.