The light harvesting systems of photosynthetic organisms harness solar energy by efficient light capture and subsequent transport of the light’s energy to a chemical reaction center. Man-made optical devices could benefit by mimicking these naturally occurring light harvesting processes. Supramolecular organic nanostructures, composed of the amphiphilic carbocyanine dye 3,3’-bis- (2-sulfopropyl)-5,5’,6,6’-tetrachloro-1,1’- dioctylbenzimida-carbocyanine (C8S3), self assemble in aqueous solution to form tubular, double-walled J-aggregates. These J-aggregates have drawn comparisons to light harvesting systems, owing to their optical and structural similarities to the cylindrical chlorosomes (antenna) from green sulfur bacteria. This research utilizes optical spectroscopy and microscopy to study the supramolecular origins of the exciton transitions and fundamental nature of exciton energy transport in C8S3 artificial light harvesting systems. Two J-aggregate morphologies are investigated: well-separated, double-walled nanotubes and bundles of agglomerated nanotubes. Linear dichroism spectroscopy of flow-aligned nanotubes is used to generate the first quantitative, polarized model for the complicated C8S3 nanotube excitonic absorption spectrum that is consistent with theoretical predictions. The C8S3 J-aggregate photophysical properties are further explored, as the Stokes shift, quantum yield, and spectral line broadening are measured as a function of temperature from 77 – 298 K. The temperature-dependent emission ratios of the C8S3 J-aggregate two-band fluorescence spectra reveal that nanotube emission is well described with Boltzmann partitioning between states, while the bundles’ is not. Finally, understanding energy transport in these materials is critical for the proposed use of artificial light harvesting systems in optoelectronic devices. The spatial extent of energy transfer in individual C8S3 J- aggregate structures is directly determined using fluorescence imaging. We find that aggregate structural hierarchy greatly influences exciton transport distances: impressive average exciton migration distances of ~ 150 nm are measured along the nanotubes, while these distances increase to over 500 nm in the bundle superstructures. / text

<p dir="ltr">Long-range exciton transport, when coupled with reduced exciton-exciton annihilation (EEA), is pivotal for the enhanced performance of organic photovoltaics and the efficiency of natural light-harvesting systems. This thesis explores strategies to optimize exciton transport and EEA rates in molecular materials by manipulating the quantum nature of excitons, particularly exciton delocalization. In addition, we also aim to understand factors limiting the transport of delocalized excitons within molecular materials. To this end, self-assembled perylene diimide (PDI) molecular aggregates are ideal candidates for this study due to their conducive properties for engineering exciton delocalization. <b>Chapter 1 </b>establishes a fundamental understanding of exciton delocalization, outlining strategies to tune this phenomenon within PDI aggregates and presenting the open questions this thesis addresses. <b>Chapter 2 </b>details the synthesis of PDI aggregates and delineates the spectroscopic techniques used for characterization, including steady-state absorption and emission, transient photoluminescence (PL), and transient absorption spectroscopy. It also describes the microscopy methods implemented to visualize exciton transport, such as transient PL microscopy and transient absorption microscopy (TAM). <b>Chapter 3 </b>introduces the thesis's primary theme: the suppression of exciton-exciton annihilation (EEA) in molecular aggregates through quantum interference. This chapter demonstrates that the spatial phase relationship of delocalized excitons is crucial in EEA, with band bottom excitons in H aggregates exhibiting an oscillating spatial phase relationship displaying a coherent suppression of EEA. <b>Chapter 4 </b>discusses how coupling to static and dynamic disorder affects coherent exciton propagation. High spatial and temporal resolution TAM experiments, along with temperature-dependent studies, help disentangle the contributions of static and dynamic disorder to exciton transport. <b>Chapter 5 </b>delves into the concept of band shape engineering, whereby the microscopic electronic couplings within PDI aggregates are fine-tuned by altering the packing motifs to regulate exciton transport. Through low-temperature TAM experiments, this chapter illustrates how the interplay between long-range Coulombic and short-range charge transfer electronic couplings can determine exciton bandwidth and influence the coherent propagation of excitons. <b>Chapter 6 </b>provides a summary of the work and discusses future directions, paving the way for continued exploration in the field of exciton transport and interaction in molecular aggregates.</p>