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Accelerating symmetry-breaking charge separation in a perylenediimide trimer through a vibronically coherent dimer intermediate

Nature Chemistry volume 14, pages 786–793 (2022)Cite this article

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Abstract

Understanding the photophysics and photochemistry of molecular π-stacked chromophores is important for utilizing them as functional photonic materials. However, these investigations have been mostly limited to covalent molecular dimers, which can only approximate the electronic and vibronic interactions present in the higher oligomers typical of functional organic materials. Here we show that a comparison of the excited-state dynamics of a covalent slip-stacked perylenediimide dimer (2) and trimer (3) provides fundamental insights into electronic state mixing and symmetry-breaking charge separation (SB-CS) beyond the dimer limit. We find that coherent vibronic coupling to high-frequency modes facilitates ultrafast state mixing between the Frenkel exciton (FE) and charge-transfer (CT) states. Subsequently, solvent fluctuations and interchromophore low-frequency vibrations promote CT character in the coherent FE/CT mixed state. The coherent FE/CT mixed state persists in 2, but, in 3, low-frequency vibronic coupling collapses the coherence, resulting in ultrafast SB-CS between the distal perylenediimide units.

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Fig. 1: Representative photoinduced dynamics of PDI stacks.
Fig. 2: Molecular structures and steady-state results.
Fig. 3: TA spectra (narrow and broadband excitation) and analysis.
Fig. 4: fsIR spectra of 1, 2 and 3 in CD2Cl2.
Fig. 5: Vibrational coherence measurements and analysis.
Fig. 6: Potential energy surface.

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Data availability

Spectroscopic data and analysis, as well as the synthesis and characterization of 2 and 3, are available in the Supplementary Information. Source data are provided with this paper.

Code availability

Codes for analysing the broadband TA data are available from M.R.W. upon request.

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Acknowledgements

This work was supported by the US Department of Energy, Office of Science, Office of Basic Energy Sciences, under award no. DE-FG02-99ER14999 (to M.R.W.). This material is based on work supported by the National Science Foundation Graduate Research Fellowship Program under grant no. DGE-1842165 (to J.D.S.). This work made use of the IMSERC MS and NMR facility at Northwestern University, which has received support from the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF ECCS-2025633), the State of Illinois, the International Institute for Nanotechnology (IIN) and Northwestern University.

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  1. These authors contributed equally: Chenjian Lin, Taeyeon Kim.

Authors and Affiliations

  1. Department of Chemistry and Institute for Sustainability and Energy at Northwestern, Northwestern University, Evanston, IL, USA

    Chenjian Lin, Taeyeon Kim, Jonathan D. Schultz, Ryan M. Young & Michael R. Wasielewski

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Contributions

C.L. synthesized and characterized the molecules, acquired the narrowband TA data, analysed the data and prepared the manuscript. T.K. acquired the broadband TA and fsIR data, analysed the data, performed the computational studies and prepared the manuscript. J.D.S. analysed the broadband TA data. M.R.W. and R.M.Y. designed the experiments, directed the investigations and prepared the manuscript with contributions from all the authors. All authors contributed to discussions.

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Correspondence to Ryan M. Young or Michael R. Wasielewski.

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The authors declare no competing interests.

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Nature Chemistry thanks Mahesh Hariharan, Dongho Kim and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary information

Supplementary Information

Supplementary Figs. 1–55, Discussion and Tables 1–6.

Source data

Source Data Fig. 2

Steady-state absorption and fluorescence of 1, 2, and 3 in THF.

Source Data Fig. 3

Narrowband and broadband transient absorption results.

Source Data Fig. 4

Femtosecond infrared data in deuterated dichloromethane.

Source Data Fig. 5

Wavepacket data including FT power, residuals, short-time FT, and FFT filter results.

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Lin, C., Kim, T., Schultz, J.D. et al. Accelerating symmetry-breaking charge separation in a perylenediimide trimer through a vibronically coherent dimer intermediate. Nat. Chem. 14, 786–793 (2022). https://doi.org/10.1038/s41557-022-00927-y

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