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Controlling quantum-beating signals in 2D electronic spectra by packing synthetic heterodimers on single-walled carbon nanotubes

Nature Chemistry volume 9, pages 219–225 (2017)Cite this article

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Abstract

In multidimensional spectroscopy, dynamics of coherences between excited states report on the interactions between electronic states and their environment. The prolonged coherence lifetimes revealed through beating signals in the spectra of some systems may result from vibronic coupling between nearly degenerate excited states, and recent observations confirm the existence of such coupling in both model systems and photosynthetic complexes. Understanding the origin of beating signals in the spectra of photosynthetic complexes has been given considerable attention; however, strategies to generate them in artificial systems that would allow us to test the hypotheses in detail are still lacking. Here we demonstrate control over the presence of quantum-beating signals by packing structurally flexible synthetic heterodimers on single-walled carbon nanotubes, and thereby restrict the motions of chromophores. Using two-dimensional electronic spectroscopy, we find that both limiting the relative rotation of chromophores and tuning the energy difference between the two electronic transitions in the dimer to match a vibrational mode of the lower-energy monomer are necessary to enhance the observed quantum-beating signals.

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Figure 1: Synthetic routes and molecular structures of fluorescein heterodimers.
Figure 2: 2D electronic spectra showing coherent dynamics of fluorescein heterodimers in solution.
Figure 3: Power spectra of waiting time (T) dynamics of heterodimers in solution and on SWNTs.
Figure 4: 2D frequency beating maps of D24 with (left) and without (right) the SWNT environment at 487 cm−1.

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Acknowledgements

The authors thank P. Dahlberg for useful discussions. L.W., G.B.G., A.Z. and G.S.E. thank the Defense Threat Reduction Agency (Grant No. HDTRA1-10-0091), Air Force Office of Scientific Research (Grant No. FA9550-14-1-0367), Defense Advanced Research Projects Agency QuBE (Grant No. N66001-10-1-4060), National Science Foundation (NSF) MRSEC Program (Grant No. DMR 14-20709), Vannevar Bush Fellowship (ONR N00014-16-1-2513), the Alfred P. Sloan Foundation and the Camille and Henry Dreyfus Foundation for support. R.F.J. and F.Z. acknowledge support from the NSF (Grant Nos. CHE-0911180 and CHE-1048528).

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Authors and Affiliations

  1. Department of Chemistry, James Franck Institute, Institute for Biophysical Dynamics, University of Chicago, Chicago, 60637, Illinois, USA

    Lili Wang, Graham B. Griffin, Alice Zhang, Feng Zhai, Nicholas E. Williams, Richard F. Jordan & Gregory S. Engel

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  1. Lili Wang
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  3. Alice Zhang
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Contributions

L.W., G.B.G., A.Z., F.Z. and G.S.E. designed the experiment. L.W., A.Z. and F.Z. performed the synthesis and characterization. L.W. and G.B.G. performed the measurements. L.W. and N.E.W. analysed the data. L.W., G.B.G. and G.S.E. wrote the manuscript, with input from all authors. G.S.E. and R.F.J. supervised the project.

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Correspondence to Gregory S. Engel.

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Wang, L., Griffin, G., Zhang, A. et al. Controlling quantum-beating signals in 2D electronic spectra by packing synthetic heterodimers on single-walled carbon nanotubes. Nature Chem 9, 219–225 (2017). https://doi.org/10.1038/nchem.2729

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