Abstract
The photophysics of three cyanine dyes (i) 1,1‘-diethyl-2,2‘-cyanine iodide (pseudoisocyanine, PIC), (ii) 3,3‘-didodecyldithia-2,2‘-carbocyanine bromide (dye 1), and (iii) 3,3‘-diethyldithia-2,2‘-carbocyanine iodide (dye 2) have been examined by picosecond-laser photolysis in aqueous and methanolic-aqueous media. At moderately high concentration, solutions of PIC in 5 M NaCl/water contain monomers, H-aggregates, and J-aggregates; dye 1 water/methanol solutions consist mostly of monomers and H-aggregates (dimers and higher n-mers); aqueous dye 2 solutions contain only monomers and dimers. Photolysis of H- and/or J-aggregates in PIC and dye 1 cyanine solutions leads to photobleaching of the respective aggregate absorption bands and subsequently decays by biphasic kinetics. Two mechanisms are discussed for the deactivation of excited aggregates. In the first, nonradiative decay of the excited singlet states results in considerable heating of the aggregates together with their surrounding solvent shells causi...
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