EXCITED-STATE DYNAMICS OF POLYMER-BOUND J-AGGREGATES

The excited-state dynamics of polymer-bound J-aggregates formed in aqu eous mixtures of pseudoisocyanine (PIC) chloride and poly(vinyl sulfon ic acid sodium salt) (PVS) (MW almost-equal-to 11 200) have been studi ed by picosecond time-correlated single-photon counting and picosecond polarized pump-probe spectroscopy. At a concentration of 40 muM PIC a nd 5 x 10(-4) g/dL PVS, the absorption spectrum of the J-aggregate is characterized by a J-band at 565 nm with a fwhm of almost-equal-to 500 cm-1. For this particular mixture, a dye molecule is bound to each of the SO3-groups on the polymer chains. The physical size of the aggreg ate is therefore determined by the number of polymer residues (almost- equal-to 87) per chain. The fluorescence lifetime and fluorescence qua ntum yield of these J-aggregates are 17 +/- 3 ps and 0.022 +/- 0.003, respectively. The lifetime is independent of the excitation intensity. From an analysis of the photophysical parameters, we infer a coherenc e size of almost-equal-to 5 +/- 1, which is smaller than the physical size of the aggregate. The pump-probe signal at 565 nm is entirely due to bleaching and consists of a fast component, with a decay time comp arable to the fluorescence lifetime, and a slow component. The decay k inetics of the induced bleaching are independent of the excitation int ensity. The signal at 558 nm consists of an absorption component at ea rly times and a slowly decaying bleaching component at long times. The anisotropy at 565 nm was constant over the 160-ps time range of the s ignal. The kinetics are rationalized in terms of a model involving the singlet exciton states of the J-aggregate and a long-lived bottleneck state. The induced absorption at early times for excitation on the bl ue edge of the J-band is consistent with a one-exciton to two-exciton transition.