International Journal of Molecular Sciences, Vol.13, No.5, 5851-5865, 2012
Room-Temperature Fluorescence Lifetime of Pseudoisocyanine (PIC) J Excitons with Various Aggregate Morphologies in Relation to Microcavity Polariton Formation
The results of room-temperature fluorescence lifetime measurements are reported for the excitation of J aggregates (Js) of pseudoisocyanine chloride (PIC-Cl) prepared in potassium polyvinyl sulfate (PVS) polymer thin films, their aqueous solutions, and NaCl aqueous solutions. Variations of the microscopic morphologies of the aggregates were investigated. The results show that fluorescence decay features correlated to the morphology change. The observed fluorescence lifetime and quantum efficiency of PIC J aggregates (PIC-Js) in a NaCl aqueous solution were 310 ps and 28%, respectively. The lifetime of the fibril-shaped macroaggregates prepared in PVS thin films was below the instrumental time resolution of 5 ps, and the efficiency decreased to below 3%. The results indicate that PIC-Js prepared with PVS polymers have an increased nonradiative contribution to the excitation deactivation process. In particular, macro-Js with isolated fibril-shaped structures revealed nonradiative pathway(s) that are closely associated to the specific packaging morphology of the constituent meso-Js. The possibility of a destructive effect on the formation of cavity-polaritons is also discussed.
Keywords:J aggregates;PIC-Cl;fluorescence decay time;fluorescence quantum efficiency;fibril-shaped macro-aggregates;Frenkel exciton;cavity polariton;dephasing