Rotational diffusion of coumarins in aqueous DMSO

The rotational dynamics of four structurally similar polar molecules viz., coumarin 440, coumarin 450, coumarin 466 and coumarin 151 has been studied in binary mixtures comprising of dimethyl sulphoxide and water at room temperature using the steady state fluorescence depolarization method and time correlated single photon counting technique. The binary mixtures are characterized by the fact that at a particular composition the viscosity (eta) of the solution reaches a maximum value that is higher than the viscosities of either of the two co-solvents. The dielectric properties of the solution change across the composition range and the qualitative features of the solvent relaxation dynamics in complex systems are known to differ from those in simple solutions. A hook type profile of rotational reorientation time (tau(r)) vs viscosity (eta) is obtained for all the solutes in dipolar aprotic mixture of dimethyl sulphoxide-water, with the rotational reorientation times being longer in organic solvent-rich zone, compared to the corresponding isoviscous point in water-rich zone due to strong hydrogen bonding. Fluorescence lifetimes as well as rotational reorientation times are sensitive to the composition of the binary solvent system under study than to the viscosity suggesting the importance of local structure. The results are discussed in the light of hydrodynamic and dielectric friction models.