Supramolecular assemblies that interact with light have recently garnered much interest as well-defined nanoscale materials for electronic excitation energy collection and transport. However, to control such complex systems it is essential to understand how their various parts interact and whether these interactions result in coherently shared excited states (excitons) or in diffusive energy transport between them. Here, we address this by studying a model system consisting of two concentric cylindrical dye aggregates in a light-harvesting nanotube. Through selective chemistry we are able to unambiguously determine the supramolecular origin of the observed excitonic transitions. These results required the development of a new theoretical model of the supramolecular structure of the assembly. Our results demonstrate that the two cylinders of the nanotube have distinct spectral responses and are best described as two separate, weakly coupled excitonic systems. Understanding such interactions is critical to the control of energy transfer on a molecular scale, a goal in various applications ranging from artificial photosynthesis to molecular electronics.
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The authors thank H. von Berlepsch and C. Böttcher for the cryoTEM images, S. Kirstein, C. M. Weber, E. Poblenz and M. Glaz for helpful discussions and laboratory assistance and A. Stradomska and V. A. Malyshev for helpful discussions. This work was supported by the Deutsche Forschungsgemeinschaft (Sfb 448 and Sfb 951), the Integrative Research Institute for the Sciences IRIS Adlershof (Berlin), the National Science Foundation (CHE-1012790), the Alexander von Humboldt-Foundation; D.M.E., S.M.V., R.J.S., M.G.B. were partially supported as part of the DOE Center for Excitonics (an Energy Frontiers Research Center funded by the US Department of Energy, Office of Science, Office of Basic Energy Sciences, DE-SC0001088), an ARO grant (W911NF-09-0480) and a DARPA grant (N66001-10-1-4063).
The authors declare no competing financial interests.
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Eisele, D., Cone, C., Bloemsma, E. et al. Utilizing redox-chemistry to elucidate the nature of exciton transitions in supramolecular dye nanotubes. Nature Chem 4, 655–662 (2012). https://doi.org/10.1038/nchem.1380
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