Abstract
Efficient transport of excitation energy over long distances is a key process in light-harvesting systems, as well as in molecular electronics1,2,3. However, in synthetic disordered organic materials, the exciton diffusion length is typically only around 10 nanometres (refs 4, 5), or about 50 nanometres in exceptional cases6,7, a distance that is largely determined by the probability laws of incoherent exciton hopping. Only for highly ordered organic systems has the transport of excitation energy over macroscopic distances been reported—for example, for triplet excitons in anthracene single crystals at room temperature8, as well as along single polydiacetylene chains embedded in their monomer crystalline matrix at cryogenic temperatures (at 10 kelvin, or −263 degrees Celsius)9. For supramolecular nanostructures, uniaxial long-range transport has not been demonstrated at room temperature. Here we show that individual self-assembled nanofibres with molecular-scale diameter efficiently transport singlet excitons at ambient conditions over more than four micrometres, a distance that is limited only by the fibre length. Our data suggest that this remarkable long-range transport is predominantly coherent. Such coherent long-range transport is achieved by one-dimensional self-assembly of supramolecular building blocks, based on carbonyl-bridged triarylamines10, into well defined H-type aggregates (in which individual monomers are aligned cofacially) with substantial electronic interactions. These findings may facilitate the development of organic nanophotonic devices and quantum information technology.
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References
Scholes, G. D., Mirkovic, T., Turner, D. B., Fassioli, F. & Buchleitner, A. Solar light harvesting by energy transfer: from ecology to coherence. Energy Environ. Sci. 5, 9374–9393 (2012)
Laquai, F., Park, Y.-S., Kim, J.-J. & Basché, T. Excitation energy transfer in organic materials: from fundamentals to optoelectronic devices. Macromol. Rapid Commun. 30, 1203–1231 (2009)
Siebbeles, L. D. A. & Grozema, F. C. (eds) Charge and Exciton Transport Through Molecular Wires. (Wiley–VCH, 2011)
Menke, S. M. & Holmes, R. J. Exciton diffusion in organic photovoltaic cells. Energy Environ. Sci. 7, 499–512 (2014)
Lin, J. D. A. et al. Systematic study of exciton diffusion length in organic semiconductors by six experimental methods. Mater. Horiz. 1, 280–285 (2014)
Bolinger, J. C., Traub, M. C., Adachi, T. & Barbara, P. F. Ultralong-range polaron-induced quenching of excitons in isolated conjugated polymers. Science 331, 565–567 (2011)
Vogelsang, J., Adachi, T., Brazard, J., Vanden Bout, D. A. & Barbara, P. F. Self-assembly of highly ordered conjugated polymer aggregates with long-range energy transfer. Nature Mater. 10, 942–946 (2011)
Avakian, P. & Merrifield, R. E. Experimental determination of the diffusion length of triplet exciton in anthracene crystals. Phys. Rev. Lett. 13, 541–543 (1964)
Dubin, F. et al. Macroscopic coherence of a single exciton state in an organic quantum wire. Nature Phys. 2, 32–35 (2006)
Haedler, A. T. et al. Synthesis and photophysical properties of multichromophoric carbonyl-bridged triarylamines. Chem. Eur. J. 20, 11708–11718 (2014)
Aida, T., Meijer, E. W. & Stupp, S. I. Functional supramolecular polymers. Science 335, 813–817 (2012)
Seki, S., Saeki, A., Sakurai, T. & Sakamaki, D. Charge carrier mobility in organic molecular materials probed by electromagnetic waves. Phys. Chem. Chem. Phys. 16, 11093–11113 (2014)
Sengupta, S. & Würthner, F. Chlorophyll J-aggregates: from bioinspired dye stacks to nanotubes, liquid crystals, and biosupramolecular electronics. Acc. Chem. Res. 46, 2498–2512 (2013)
Cantekin, S., de Greef, T. F. A. & Palmans, A. R. A. Benzene-1,3,5-tricarboxamide: a versatile ordering moiety for supramolecular chemistry. Chem. Soc. Rev. 41, 6125–6137 (2012)
Dou, X., Pisula, W., Wu, J., Bodwell, G. J. & Müllen, K. Reinforced self-assembly of hexa-peri-hexabenzocoronenes by hydrogen bonds: from microscopic aggregates to macroscopic fluorescent organogels. Chem. Eur. J. 14, 240–249 (2008)
Scheibe, G., Schöntag, A. & Katheder, F. Fluoreszenz und Energiefortleitung bei reversibel polymerisierten Farbstoffen. Naturwissenschaften 29, 499–501 (1939)
Eisele, D. M., Knoester, J., Kirstein, S., Rabe, J. P. & Vanden Bout, D. A. Uniform exciton fluorescence from individual molecular nanotubes immobilized on solid substrates. Nature Nanotechnol. 4, 658–663 (2009)
Clark, K. A., Krueger, E. L. & Vanden Bout, D. A. Direct measurement of energy migration in supramolecular carbocyanine dye nanotubes. J. Phys. Chem. Lett. 5, 2274–2282 (2014)
Lin, H. et al. Collective fluorescence blinking in linear J-aggregates assisted by long-distance exciton migration. Nano Lett. 10, 620–626 (2010)
Zhang, W. et al. Supramolecular linear heterojunction composed of graphite-like semiconducting nanotubular segments. Science 334, 340–343 (2011)
Winiger, C. B., Li, S., Kumar, G. R., Langenegger, S. M. & Häner, R. Long-distance electronic energy transfer in light-harvesting supramolecular polymers. Angew. Chem. Int. Ed. 53, 13609–13613 (2014)
Eisele, D. M. et al. Robust excitons inhabit soft supramolecular nanotubes. Proc. Natl Acad. Sci. USA 111, E3367–E3375 (2014)
Kasha, M., Rawls, H. R. & Ashraf El-Bayoumi, M. The exciton model in molecular spectroscopy. Pure Appl. Chem. 11, 371–392 (1965)
Chaudhuri, D. et al. Enhancing long-range exciton guiding in molecular nanowires by H-aggregation lifetime engineering. Nano Lett. 11, 488–492 (2011)
Field, J. E. & Venkataraman, D. Heterotriangulenes—structure and properties. Chem. Mater. 14, 962–964 (2002)
Kivala, M. et al. Columnar self-assembly in electron-deficient heterotriangulenes. Chem. Eur. J. 19, 8117–8128 (2013)
Spano, F. C. Modeling disorder in polymer aggregates: the optical spectroscopy of regioregular poly(3-hexylthiophene) thin films. J. Chem. Phys. 122, 234701 (2005)
Scheblykin, I. G., Sliusarenko, O. Y., Lepnev, L. S., Vitukhnovsky, A. G. & Van der Auweraer, M. Strong nonmonotonous temperature dependence of exciton migration rate in J aggregates at temperatures from 5 to 300 K. J. Phys. Chem. B 104, 10949–10951 (2000)
Cogdell, R. J., Gall, A. & Köhler, J. The architecture and function of the light-harvesting apparatus of purple bacteria: from single molecules to in vivo membranes. Q. Rev. Biophys. 39, 227–324 (2006)
Oostergetel, G. T., van Amerongen, H. & Boekema, E. J. The chlorosome: a prototype for efficient light harvesting in photosynthesis. Photosynth. Res. 104, 245–255 (2010)
Issac, A. et al. Single molecule studies of calix[4]arene-linked perylene bisimide dimers: relationship between blinking, lifetime and/or spectral fluctuations. Phys. Chem. Chem. Phys. 14, 10789–10798 (2012)
Issac, A., Hildner, R., Hippius, C., Würthner, F. & Köhler, J. Stepwise decrease of fluorescence versus sequential photobleaching in a single multichromophoric system. ACS Nano 8, 1708–1717 (2014)
Acknowledgements
We acknowledge financial support from the Bavarian State Ministry of Science, Research, and the Arts for the Collaborative Research Network ‘Solar Technologies go Hybrid’, the Deutsche Forschungsgemeinschaft (DFG) within projects GRK1640 (A.T.H., A.I., B.W., J.K., H.-W.S., R.H.) HI1508/2 (R.H.), and SFB953 ‘Synthetic Carbon Allotropes’ (M.K., N.H.), and the Cluster of Excellence ‘Engineering of Advanced Materials’ (EAM) at the University of Erlangen-Nürnberg (M.K., N.H.). A.T.H. was funded by the ‘Macromolecular Science’ elite study program at the University of Bayreuth and an ‘Elite Netzwerk Bayern’ fellowship. We thank A. Schedl, M. Hund and M. Drechsler for their support with AFM and TEM.
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A.T.H., K.K. and H.-W.S. designed and prepared compounds 1 and 2, and investigated their self-assembly. M.K. and N.H. synthesized the functionalized CBT core as a building block for the synthesis of compounds 1 and 2. R.H., A.I., B.W. and J.K. designed and performed optical experiments on single nanofibres. All authors contributed to discussion of the data and writing of the manuscript.
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Haedler, A., Kreger, K., Issac, A. et al. Long-range energy transport in single supramolecular nanofibres at room temperature. Nature 523, 196–199 (2015). https://doi.org/10.1038/nature14570
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DOI: https://doi.org/10.1038/nature14570
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