Quenching of the triplet state of safranine-O by aliphatic amines in AOT reverse micelles studied by transient absorption spectroscopy

Abstract

The photophysics of Safranine-O (3,6-diamino-2,7-dimethyl-5 phenyl phenazinium chloride) (SfH+Cl-) was investigated in reverse micelles (RMs) of AOT (sodium bis(2-ethylhexyl) sulfosuccinate) with special emphasis on the triplet state processes. The excited singlet state properties were measured by absorption and fluorescence spectroscopy. Steady state anisotropy was also measured as a function of the water content. All the measurements indicate that the dye is localized in the interface, sensing a medium of polarity similar to EtOH:water (3:1) mixtures. The triplet is formed in its monoprotonated form, independently of the pH of the water used to prepare the RMs. The maximum of the T-T absorption spectrum in RMs confirms this conclusion. The triplet lifetime is much longer in AOT RMs than in homogeneous organic solvents. The intersystem crossing quantum yields are similar to those in organic solvents. A remarkable difference is observed in the quenching by aliphatic amines, while the quenching by the hydrophobic tributylamine is similar to that in methanol, the hydro-soluble triethanolamine is one order of magnitude more effective in RMs than in homogeneous solution. In the latter case the quenching process is interpreted by a very fast intramicellar quenching, the overall kinetics being controlled by the exchange of amine molecules between RMs. Semireduced dye is formed in the quenching process in RMs in the di-protonated state with a comparable quantum yield to the monoprotonated state formed in homogeneous solvents. The results point to the advantage of the reverse micellar system for the generation of active radicals for the initiation of vinyl polymerization, since a much lower concentration of amine can be employed with similar quantum yields.