Exciton Migration in Multistranded Perylene Bisimide J-Aggregates

Exciton migration in self-assembled supramolecular ensembles of dye molecules is controlled by the electronic coupling between adjacent sites, the delocalization of the excitation and thereby by the packing arrangement. Here, we put emphasis on the packing structure and analyze the exciton migration in two perylene bisimide-based J-aggregates composed of almost identical molecular building blocks but forming double-strand versus quadruple-strand slip-stacked supramolecular architectures. Analyzing ultrafast transient absorption spectra in dependence on the exciton density by a kinetic model for exciton-exciton annihilation based on incoherent transfer demonstrates that the migration is quasi one-dimensional. The migration distance is enhanced by a beneficial geometrical structure. We find a factor of more than two between the diffusion lengths of 188 and 77 nm for the double- and quadruple-stranded system. The supramolecular design efficiently influences the exciton mobility and minor structural changes have a pronounced influence on functional properties of dye aggregates.