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Supramolecular dyads as photogenerated qubit candidates

Nature Chemistry volume 17, pages 493–499 (2025)Cite this article

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Abstract

Molecular spin qubits have the advantages of synthetic flexibility and amenability to be tailored to specific applications. Among them, chromophore–radical systems have emerged as appealing qubit candidates. These systems can be initiated by light to form triplet–radical pairs that can result in the formation of quartet states by spin mixing. For a triplet–radical pair to undergo spin mixing, the molecular bridge joining the spin centres must permit effective spin communication, which has previously been ensured using covalent, π-conjugated linkers. Here we used perylenediimides and nitroxide radicals designed to self-assemble in solution via hydrogen bonding and observed, using electron paramagnetic resonance spectroscopy, the formation of quartet states that can be manipulated coherently using microwaves. This unprecedented finding that non-covalent bonds can enable spin mixing advances supramolecular chemistry as a valuable tool for exploring, developing and scaling up materials for quantum information science.

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Fig. 1: Influence of the linker on the formation of quartet states in photogenerated triplet–radical systems.
Fig. 2: Self-assembly properties of the PDI···TZ systems.
Fig. 3: Transient pulse EPR spectra.
Fig. 4: Transient pulse nutation data and the corresponding Fourier transform.
Fig. 5: Transient Rabi oscillations for PDI–H···TZ–eTEMPO.

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The data supporting the findings of this study are available within the article and Supplementary Information. Source data are provided with this paper.

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Acknowledgements

This work was supported by the Interdisciplinary Thematic Institute SysChem via IdEx Unistra (ANR-10-IDEX-0002) within the programme Investissement d’Avenir (A.V.J.), the Agence Nationale de la Recherche (ANR; French National Research Agency, project no. ANR-24-CE92-0009-01, to A.V.J.), the Deutsche Forschungsgemeinschaft (DFG; German Research Foundation, project nos. 417643975 and 545606231, S.R.) and the Fonds der Chemischen Industrie (FCI; S.R.). We thank the SIBW/DFG for financing the EPR instrumentation that is operated within the MagRes Center of the University of Freiburg (grant no. INST 39/928-1 FUGG) and acknowledge support by the Cluster de cAlcul Intensif à l’Université de Strasbourg (CAIUS) by providing access to computing resources. A.V.J. acknowledges support by the CNRS via the Emergence@INC programme.

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Author notes

  1. These authors contributed equally: Ivan V. Khariushin, Philipp Thielert.

Authors and Affiliations

  1. SAMS Research Group, Université de Strasbourg, CNRS, Institut Charles Sadron UPR 22, Strasbourg, France

    Ivan V. Khariushin & Andreas Vargas Jentzsch

  2. Institute of Physical Chemistry, University of Freiburg, Freiburg, Germany

    Philipp Thielert, Elisa Zöllner, Maximilian Mayländer, Theresia Quintes & Sabine Richert

Authors
  1. Ivan V. Khariushin
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  2. Philipp Thielert
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  4. Maximilian Mayländer
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  7. Andreas Vargas Jentzsch
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Contributions

I.V.K. synthesized the compounds and characterized the self-assembly by UV–visible and NMR spectroscopy; P.T. performed the EPR measurements and analysed the EPR data with help from E.Z.; E.Z. performed the variable-temperature UV–visible measurements; M.M. performed the initial EPR experiments; T.Q. and E.Z. simulated the EPR data; S.R. supervised the EPR studies; A.V.J. supervised the synthesis and characterization of the compounds and carried out DFT calculations; S.R. and A.V.J. conceived the study and wrote the paper with the help of all of the co-authors.

Corresponding authors

Correspondence to Sabine Richert or Andreas Vargas Jentzsch.

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Nature Chemistry thanks Malcolm Forbes, Natia Frank 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 Discussion, extended discussion of the experimental procedures, Figs. 1–33 and Tables 1–5.

Supplementary Data 1

xyz coordinates for the optimized DFT structures.

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Source Data Fig. 2

ASCII data for Fig. 2.

Source Data Fig. 3

ASCII data for Fig. 3.

Source Data Fig. 4

ASCII data for Fig. 4.

Source Data Fig. 5

ASCII data for Fig. 5.

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Khariushin, I.V., Thielert, P., Zöllner, E. et al. Supramolecular dyads as photogenerated qubit candidates. Nat. Chem. 17, 493–499 (2025). https://doi.org/10.1038/s41557-024-01716-5

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