Estimation the dielectric properties of solvation shells and nano-cavities by solvatochromic shift of organic dye

Abstract

We investigated the preferential solvation effect of pyridinium-N-phenolate betaine (organic dye) taken as a molecular probe in two binary solvents (water-BuOH and water-BuNH2) in concentration range 0-100%. The Onsager-Liptay model was used to connect the spectral solvatochromic shift in solvation shell of the dye with the dielectric permittivity of the environment around its chromophore. That makes it possible to estimate the effective dielectric constant in the microscopic region of the probe, based on the values of the experimentally measured solvatochromic shifts. It was shown that the solvation shell of the dye is significantly depleted with the second component of binary solvent in water solution. It is true both for the water-BuOH and water-BuNH2 solvents. The absolute spectral shift in case of water-BuNH2 solvent is greater than in the second case. However, the relative depletion is stronger in case of water-BuOH. The innovative potential of the method is in the development the nanoprobe devices to measure the dielectric constant of small objects and nano-regions, to control instantaneous solvent concentration into evaporating sessile droplet of binary solvent in different zones of the droplet.