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Electric field modulation of magnetic exchange in molecular helices


The possibility to operate on magnetic materials through the application of electric rather than magnetic fields—promising faster, more compact and energy efficient circuits—continues to spur the investigation of magnetoelectric effects. Symmetry considerations, in particular the lack of an inversion centre, characterize the magnetoelectric effect. In addition, spin–orbit coupling is generally considered necessary to make a spin system sensitive to a charge distribution. However, a magnetoelectric effect not relying on spin–orbit coupling is appealing for spin-based quantum technologies. Here, we report the detection of a magnetoelectric effect that we attribute to an electric field modulation of the magnetic exchange interaction without atomic displacement. The effect is visible in electron paramagnetic resonance absorption of molecular helices under electric field modulation and confirmed by specific symmetry properties and spectral simulation.

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Fig. 1: Structure and spin–electric properties of the MnPhOMe molecular helices.
Fig. 2: Magnetic properties of the MnPhOMe molecular helices.
Fig. 3: Numerical simulation of experimental set-up for EFM-EPR.
Fig. 4: EFM-EPR spectra.

Data availability

All relevant data, including ASCII files of the recorded spectra, are available from the authors on request.


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The financial support was from Italian MIUR through the PRIN 2015 HYFSRT project, from European QuantERA through the SUMO project and from Fondazione CR Firenze. M.F. is grateful to M. Carlà and G. Aloisi for useful discussion and practical assistance, to E. Goovaerts for sharing the initial idea of performing EPR on selected samples by using an electric field, to G. Tobia, who assembled the sample holder, and to A. Orlando for technical assistance. F. La Mattina is acknowledged for seminal discussions on EFM-EPR technique and S. Ciattini for assistance in X-ray characterization. We thank S. Picozzi and M. Scarrozza for having stimulated this research with their seminal theoretical work on this type of magnetoelectric effect. L. Sorace is acknowledged for critical reading of the manuscript.

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Authors and Affiliations



M.F. and R.S. conceived the research. A. Caneschi synthesized the materials and grew the crystals. M.F. and G.A. designed the EFM-EPR set-up with assistance of A.V. G.A. simulated the electric field distribution and calculated the oscillating magnetic field. A. Cini and M.F. recorded and simulated the EPR spectra; A.V. developed the model for the analysis of magnetic data collected by R.S. M.F., A. Cini and R.S. wrote the manuscript with contributions from all authors.

Corresponding authors

Correspondence to Maria Fittipaldi or Roberta Sessoli.

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Supplementary Information

Supplementary Figures 1–10, Supplementary Tables 1–2, Supplementary Notes 1–4, Supplementary References 1–9

Supplementary Video 1

Electric field versus magnetic field modulated EPR: this video illustrates why a derivative signal with variable phase is detected when recording the EPR absorption under the modulation of the electric field.

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Fittipaldi, M., Cini, A., Annino, G. et al. Electric field modulation of magnetic exchange in molecular helices. Nat. Mater. 18, 329–334 (2019).

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