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Frenkel excitons in heat-stressed supramolecular nanocomposites enabled by tunable cage-like scaffolding

Nature Chemistry volume 12, pages 1157–1164 (2020)Cite this article

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Abstract

Delocalized Frenkel excitons—coherently shared excitations among chromophores—are responsible for the remarkable efficiency of supramolecular light-harvesting assemblies within photosynthetic organisms. The translation of nature’s design principles to applications in optoelectronic devices has been limited by the fragility of the supramolecular structures used and the delicate nature of Frenkel excitons, particularly under mildly changing solvent conditions and elevated temperatures and upon deposition onto solid substrates. Here, we overcome those functionalization barriers through composition of stable supramolecular light-harvesting nanotubes enabled by tunable (~4.3–4.9 nm), uniform (±0.3 nm) cage-like scaffolds. High-resolution cryogenic electron microscopy, combined with scanning electron microscopy, broadband femtosecond transient absorption spectroscopy and near-field scanning optical microscopy revealed that excitons within the cage-like scaffolds are robust, even under extreme heat stress, and control over nanocomposite dimensions is maintained on solid substrates. Our bio-inspired nanocomposites provide a general framework for the development of next-generation organic devices made from stable supramolecular materials.

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Fig. 1: Supramolecular LHNTs assembled from the cyanine dye derivative C8S3.
Fig. 2: Stable supramolecular nanocomposites via cage-like scaffold design.
Fig. 3: Robust Frenkel excitons in supramolecular nanocomposites despite extreme heat stress.
Fig. 4: Discrete tunability of supramolecular nanocomposites’ scaffold dimensions in solution and on substrate.

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The data that support the findings of this study are available from the corresponding author upon reasonable request. Source data are provided with this paper.

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Acknowledgements

This material is based on work partially supported by the National Science Foundation (NSF) Faculty Early Career Development Program (NSF-CAREER 1752475) and US Department of Energy, Office of Science, Office of Basic Energy Sciences. Equipment support was partially provided by the NSF Major Research Instrumentation Program (NSF-MRI 1531859). Financial support for the time-resolved spectroscopic studies was partially provided by the US Department of Energy, Office of Science, Office of Basic Energy Sciences (DE-SC0018142). Support for the solar cell design and fabrication was partially provided by the NSF-CREST Center for Interface Design and Engineered Assembly of Low Dimensional Systems (IDEALS) (NSF grant HRD-1547830). D.M.E., N.V. and P.G. acknowledge partial support from the US Department of Energy, Office of Science, Office of Basic Energy Sciences (DE-SC0018142). M.W. acknowledges support from the NSF-CREST IDEALS Fellowship. W.P.C. acknowledges partial support from the Margaret Strauss Kramer Fellowship. S.J.J. is supported by the NSF (CHE-1900170) and the US Department of Energy, Office of Sciences, Office of Basic Energy Sciences (DE-SC0001393). This work was performed in part at the Center for Discovery and Innovation (CDI) of The City College of New York and the Advanced Science Research Center (ASRC) Imaging Facility of The City University of New York. We thank the Martin and Michele Cohen Fund for Science, the PSC-CUNY Research Award Program, WITec GmbH, Tavid Ezell, David M. Milch and Tony Liss for generous support.

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Authors and Affiliations

  1. PhD Program in Chemistry, Graduate Center, The City University of New York, New York, NY, USA

    Kara Ng, Pooja Gaikwad, Ilona Kretzschmar & Dorthe M. Eisele

  2. Department of Chemistry and Biochemistry, The City College of New York at The City University of New York, New York, NY, USA

    Kara Ng, William P. Carbery, Nikunjkumar Visaveliya, Pooja Gaikwad & Dorthe M. Eisele

  3. Department of Chemical Engineering, The City College of New York at The City University of New York, New York, NY, USA

    Megan Webster & Ilona Kretzschmar

  4. Department of Chemistry, New York University, New York, NY, USA

    William P. Carbery

  5. Department of Chemistry and Biochemistry, Queens College at The City University of New York, New York, NY, USA

    Seogjoo J. Jang

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Contributions

D.M.E. directed the project. K.N. synthesized the samples, performed the ensemble, cryo-TEM and NSOM measurements and temperature-dependent studies, analysed the experimental data, initiated collaboration with M.W. and I.K. and prepared the samples for linear sweep voltammetry measurements. N.V. and P.G. prepared samples for the time-resolved spectroscopy experiments, N.V. performed the SEM measurements, and W.P.C. and K.N. performed the time-resolved spectroscopy measurements and analysed the experimental data. K.N. and M.W. designed and fabricated the DSSCs under the guidance of I.K. and K.N. analysed the experimental data under the guidance of D.M.E. S.J.J. contributed to the interpretation of spectroscopic data of heat-stressed samples. All authors provided fruitful discussions and beneficial interpretation of the data and analyses. K.N. and D.M.E. co-wrote the manuscript with input from all authors.

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Correspondence to Dorthe M. Eisele.

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Ng, K., Webster, M., Carbery, W.P. et al. Frenkel excitons in heat-stressed supramolecular nanocomposites enabled by tunable cage-like scaffolding. Nat. Chem. 12, 1157–1164 (2020). https://doi.org/10.1038/s41557-020-00563-4

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