The effect of intermolecular electronic coupling on the exciton dynamics in perylene red nanoparticles

Understanding the transport mechanisms of electronic excitations in molecular systems is the basis for their application in light harvesting and opto-electronic devices. The exciton transfer properties depend pivotally on the intermolecular coupling and the latter on the supramolecular structure. In this work, organic nanoparticles of the perylene derivative Perylene Red are prepared with flash-precipitation under different conditions. We correlate their intermolecular couplings, optical spectra, quantum yields, emission lifetimes and their size and characterize their exciton dynamics upon excitation with ultrashort laser pulses by transient absorption spectroscopy. We find that the intermolecular coupling can be varied by changing the preparation conditions and thus the supramolecular structure. In contrast to the monomeric system, the generation of charge-transfer states is found after optical excitation of the nanoparticles. The time of the generation step is in the order of 100 ps and depends on the intermolecular coupling. The mobility of the originally excited excitons is determined from measurements with varying exciton density. To this end, we model the contribution of exciton-exciton annihilation to the exciton decay assuming three-dimensional incoherent diffusion. The extracted exciton diffusion constant of nanoparticles with stronger intermolecular coupling is found to be 0.17 nm² ps⁻¹ and thereby about ten times higher than in the particles with smaller coupling.