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Enabling singlet fission by controlling intramolecular charge transfer in π-stacked covalent terrylenediimide dimers

Nature Chemistry volume 8, pages 1120–1125 (2016)Cite this article

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Abstract

When an assembly of two or more molecules absorbs a photon to form a singlet exciton, and the energetics and intermolecular interactions are favourable, the singlet exciton can rapidly and spontaneously produce two triplet excitons by singlet fission. To understand this process is important because it may prove to be technologically significant for enhancing solar-cell performance. Theory strongly suggests that charge-transfer states are involved in singlet fission, but their role has remained an intriguing puzzle and, up until now, no molecular system has provided clear evidence for such a state. Here we describe a terrylenediimide dimer that forms a charge-transfer state in a few picoseconds in polar solvents, and undergoes equally rapid, high-yield singlet fission in nonpolar solvents. These results show that adjusting the charge-transfer-state energy relative to those of the exciton states can serve to either inhibit or promote singlet fission.

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Figure 1: Steady-state characterization of TDI systems.
Figure 2: Transient absorption spectra of TDI systems in CH2Cl2.
Figure 3: Triplet characterization in TDI dimer 2.
Figure 4
Figure 5: Proposed schematic potential-energy surface of SF.

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Acknowledgements

This work was supported by the Chemical Sciences, Geosciences, and Biosciences Division, Office of Basic Energy Sciences, US Department of Energy (DOE) under Grant No. DE-FG02-99ER14999 (M.R.W.). The authors thank R. D. Schaller for performing phosphorescence measurements. G.C.S. was supported by the Argonne-Northwestern Solar Energy Research (ANSER) Center, an Energy Frontier Research Center funded by the Office of Science, Office of Basic Energy Sciences, US DOE, under award number DE-SC0001059.

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Authors and Affiliations

  1. Department of Chemistry and Argonne-Northwestern Solar Energy Research (ANSER) Center, Northwestern University, Evanston, 60208-3113, Illinois, USA

    Eric A. Margulies, Claire E. Miller, Yilei Wu, Lin Ma, George C. Schatz, Ryan M. Young & Michael R. Wasielewski

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  1. Eric A. Margulies
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Contributions

E.A.M. synthesized the molecules, analysed the data and prepared the manuscript, C.E.M. acquired the fsTA data and performed the computational studies, Y.W. performed the redox titration experiments, L.M. performed the TRF measurements, R.M.Y. analysed the fsTA data. G.C.S. directed the computational modelling. M.R.W. designed the experiments, directed the investigations and prepared the manuscript with contributions from all the authors; all the authors contributed to discussions.

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Correspondence to Michael R. Wasielewski.

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Margulies, E., Miller, C., Wu, Y. et al. Enabling singlet fission by controlling intramolecular charge transfer in π-stacked covalent terrylenediimide dimers. Nature Chem 8, 1120–1125 (2016). https://doi.org/10.1038/nchem.2589

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