Spectroscopic characterization of phenazinium dye aggregates in water and acetonitrile media: effect of methyl substitution on the aggregation phenomenon.

Absorption, fluorescence, and fluorescence excitation spectral studies of two planar, cationic phenazinium dyes, namely, phenosafranin (PSF) and safranin-T (ST), have been performed in protic and aprotic polar solvents. The studies reveal the formation of both J- and H-aggregates in concentrated solutions. The planarity of the phenazinium skeleton and the presence of a positive charge are attributed to be the driving force for this aggregation behavior. The aggregates are established to be dimers only. The positive inductive effect of the methyl substituents in safranin-T augments the aggregation process. The experiments reveal that for both dyes, the polar protic solvent favors the aggregation process more than the aprotic solvent.