Enhancement of exciton transport in porphyrin aggregate nanostructures by controlling the hierarchical self-assembly

Abstract

Exciton transport in meso-tetra(4-sulfonatophenyl) porphyrin (TPPS) J-aggregates was directly imaged using the emission profile analysis method with confocal fluorescence microscopy. By controlling the structural hierarchy of TPPS aggregates, we could comparatively study the exciton transport properties in single nanotubes and bundled structures. Using the one-dimensional diffusion model, the exciton diffusion coefficients of TPPS nanotubes and bundles were estimated as 95 and 393 nm² ps⁻¹, respectively, showing a dramatic enhancement of exciton transport in bundled structures. To reveal the underlying mechanism of enhanced exciton transport in bundle compared to that in single strands, the spatially resolved measurements of exciton transport images were correlated with the spectral information at each local sites. We have confirmed that nanotube and its bundled form possess different energetic landscapes and exciton migration dynamics. Agglomeration into bundles led to an increase in system-environment coupling and denser distribution of energy states, facilitating longer migration length and accelerated transport. Detailed analysis in this study provides important insights into the structure-dependent exciton transport properties of self-assembled J-aggregate nanostructures.