Effect of Polymethylene Spacer of Cationic Gemini Surfactants on Solvation Dynamics and Rotational Relaxation of Coumarin 153 in Aqueous Micelles.

The present work demonstrates the solvation dynamics and rotational relaxation of Coumarin 153 (C-153) in the micelles of a series of cationic gemini surfactants, 12-s-12, 2Br(-) containing a hydrophobic polymethylene spacer with s = 3, 4, 6, 8, 12. Steady-state and time-correlated single-photon counting (TCSPC) fluorescence spectroscopic techniques have been used to carry out this study. Steady-state and TCSPC fluorescence data suggest that C-153 molecules are located at the Stern layer of micelles. While probe molecules feel more or less the same micropolarity in the micellar phase, the microviscosity of micelles decreases with spacer chain length. Solvation dynamics at the Stern layer is bimodal in nature with fast solvation as a major component. Counter ions and water molecules bonded with the polar headgroups of surfactant molecules are responsible for the slow component. Average solvation time increases with spacer chain length because of the increased degree of counter ion dissociation. Some water molecules are involved in the solvation of counter ions themselves, resulting in the decrease in "free" water molecules to be available for the solvation of C-153. The hydrophobic spacer chain also has an effect on increasing the solvation time with increasing chain length. The average rotational relaxation time for C-153 decreases with spacer chain length with a rapid decrease at s > 4. The anisotropy decay of C-153 in micelles is biexponential in nature. The slow rotational relaxation is due to the lateral diffusion of C-153 in micelles. Lateral diffusion is much faster than the rotational motion of a micelle as a whole. The rotational motion of the micelle as a whole becomes faster with the decreasing size of micelles.