Direct Measurement of Energy Migration in Supramolecular Carbocyanine Dye Nanotubes.

Exciton transport lengths in double-walled and bundled cylindrical 3,3'-bis- (2-sulfopropyl)-5,5',6,6'-tetrachloro-1,1'-dioctylbenzimida-carbocyanine (C8S3) J-aggregates were measured using direct imaging of fluorescence from individual aggregates deposited on solid substrates. Regions identified in confocal images were excited with a focused laser spot, and the resulting fluorescence emission was imaged onto an electron multiplying charged coupled device camera. A two-dimensional Gaussian fitting scheme was used to quantitatively compare the excitation beam profile to the broadened aggregate emission profiles. The double-walled tubes exhibit average exciton transport lengths of 140 nm, while exciton transport in the bundled nanotubes was found to be remarkably long, with distances reaching many hundreds of nanometers. A steady-state one-dimensional diffusion model for the broadening of the emission profiles yields diffusion coefficients of 120 nm(2) ps(-1) for the nanotubes and 7000 nm(2) ps(-1) for the aggregate bundles. The level of structural hierarchy dramatically affects the exciton transport capabilities in these artificial light-harvesting systems, and energy migration is not limited to a single dimension in J-aggregate bundles.