The Role of Hydrogen Bonding in the Preferential Solvation of 5-Aminoquinoline in Binary Solvent Mixtures.

Abstract

5-Aminoquinoline (5AQ) has been used as a fluorescent probe of preferential solvation (PS) in binary solvent mixtures in which the nonpolar component is diethyl ether and the polar component is protic (methanol) or aprotic (acetonitrile). Hence, the roles of solvent polarity and solute-solvent hydrogen bonding have been delineated. Positive deviations of spectral shifts from a linear dependence on the concentration of the polar component, signifying PS, are markedly more pronounced in case of the protic solvent. Solvation dynamics on a nanosecond time scale mark the formation of the solvation shell around the fluorescent probe. Time-resolved area-normalized emission spectra indicate the occurrence of the continuous solvation of the excited state when the polar component is acetonitrile. In contrast, two distinct states were observed when the polar component was methanol, the second state being the hydrogen bonded one. Translational diffusion is the rate-determining step for formation of the solvation shell. The time constant associated with it has been estimated from rise times observed in fluorescence transients monitored at the red end of the fluorescence spectra and also from the time evolution of the spectral width of time-resolved emission spectra.