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Utilizing redox-chemistry to elucidate the nature of exciton transitions in supramolecular dye nanotubes

Nature Chemistry volume 4, pages 655–662 (2012)Cite this article

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Abstract

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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Figure 1: Light-harvesting nanotube consisting of double-walled cylindrical aggregates of amphiphilic cyanine dye molecules.
Figure 2: Chemical oxidation of light-harvesting nanotubes in solution.
Figure 3: Isolated absorption spectrum of the inner-wall cylinder of the light-harvesting nanotubes.
Figure 4: Structural model for a light-harvesting nanotube and theoretical simulations of linear absorption spectra of nanotubes.
Figure 5: Comparison of theoretical simulations with experimental absorption spectra.

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Acknowledgements

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).

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Author notes

  1. R. J. Silbey: Deceased

Authors and Affiliations

  1. Center for Excitonics and Department of Chemistry, Massachusetts Institute of Technology, 77 Massachusetts Avenue, Cambridge, 02139, Massachusetts, USA

    D. M. Eisele, S. M. Vlaming, R. J. Silbey & M. G. Bawendi

  2. Department of Physics and IRIS Adlershof, Humboldt-Universität zu Berlin, Newtonstraße 15, Berlin, D-12489, Germany

    D. M. Eisele & J. P. Rabe

  3. Department of Biochemistry and Chemistry and Center for Nano and Molecular Science and Technology, University of Texas at Austin, 1 University Station A5300, Austin, 78712-0165, Texas, USA

    C. W. Cone & D. A. Vanden Bout

  4. University of Groningen, Institute for Theoretical Physics and Zernike Institute for Advanced Materials, Groningen, The Netherlands

    E. A. Bloemsma, S. M. Vlaming, C. G. F. van der Kwaak & J. Knoester

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Contributions

J.P.R., D.A.V.B., J.K. and D.M.E. developed the project. D.M.E. performed experiments and data analysis, put results into perspective, and initiated the collaborations. E.A.B., S.M.V. and C.v.d.K designed the theoretical model with guidance from J.K. E.A.B. analysed the theoretical model and performed the fit to the experimental spectra, supervised by J.K. C.W.C. performed SVD analysis under the guidance of D.A.V.B. R.J.S. and M.G.B. provided helpful discussions and beneficial interpretation of the data analysis. D.M.E., E.A.B., S.M.V., J.K., M.G.B. and D.A.V.B. co-wrote the paper, with input from the other authors.

Corresponding authors

Correspondence to J. Knoester or D. A. Vanden Bout.

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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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