Molecular Distribution Behavior of Cyanine Dyes in Aqueous Solution

The molecular distribution of the cyanine dye (5-chloro-2-[3-[5-chloro-3-(4-sulfobutyl)-2(3H)benzothiazolylidine]-1-propenyl]-3-(4-sulfobutyl)-benzothiazolium hydroxide triethylamine salt, NK-3796) in aqueous solution was investigated using absorption and emission spectroscopy. Dimers of the dye are formed in concentrated solutions, while monomers dominate more diluted solutions. J aggregates are formed in solutions containing electrolytes such as sodium chloride, calcium chloride, and di-hydrogen ammonium phosphate. The dye readily forms J aggregates upon mixing with electrolyte. The J aggregates formation was followed spectroscopically by the appearance of a red-shifted narrow band centered at 653 nm in the absorption spectra. A similar shift is also observed in the emission spectra. The absorbance bandwidth is dependent on the charge of the cation of the electrolyte. This suggests different ground-state conformations for the J aggregates in solution.