Spin-Electric Effect on a Chiral Dysprosium Complex

Year: 2025

Authors: Tacconi L., Cini A., Raza A., Tesi L., Bartolini P., Taschin A., van Slageren J., Briganti M., Sorace L., Fittipaldi M., Perfetti M.

Autors Affiliation: Univ Florence, Dept Chem Ugo Schiff, I-50019 Sesto Fiorentino, FI, Italy; INSTM Res Unit, I-50019 Sesto Fiorentino, FI, Italy; Univ Florence, Dept Phys & Astron, I-50019 Sesto Fiorentino, FI, Italy; DIEF, Dept Ind Engn, I-50139 Florence, Italy; Univ Stuttgart, Inst Phys Chem, D-70569 Stuttgart, Germany; Univ Stuttgart, Ctr Integrated Quantum Sci & Technol, D-70569 Stuttgart, Germany; CNR, INO, I-50019 Sesto Fiorentino, FI, Italy; Univ Firenze, LENS, I-50019 Florence, Italy.

Abstract: The Spin-Electric Effect (SEE) on molecules-the influence of external electric fields on molecular spin states-offers a compelling route toward low-power molecule-based spintronic applications. However, SEE remains elusive in molecular systems due to typically weak spin-electric field coupling. In this study, we observe a relevant SEE in a mononuclear lanthanide complex using Electric Field Modulated Electron Paramagnetic Resonance spectroscopy. We reveal a marked anisotropy of the SEE, evidencing that the most perturbed g tensor component is the one perpendicular to the electric field, providing hints for the most convenient experimental configuration to tune ad hoc spin transitions. Ab initio calculations in synergy with the experimental results revealed that molecular symmetry breaking plays a fundamental role. We also point out the crystal field parameters that are most strongly modulated by the presence of an electric field. These parameters are all off-diagonal, indicating effective electric-field-mediated state mixing.

Journal/Review: JOURNAL OF THE AMERICAN CHEMICAL SOCIETY

Volume: 147 (36)      Pages from: 33040  to: 33051

More Information: This work was funded by the European Union (ERC, ELECTRA, 101039890). Views and opinions expressed are however those of the author(s) only and do not necessarily reflect those of the European Union or the European Research Council. Neither the European Union nor the granting authority can be held responsible for them. The financial support provided by the MUR-Dipartimenti di Eccellenza 2023-2027 (DICUS 2.0) (ref no. B96C1700020008) to the Department of Chemistry Ugo Schiff of the University of Florence is acknowledged. The Departmental facility CRIST at the University of Florence is kindly acknowledged for helping with crystal structure resolution. M.F. is grateful to Giampaolo Tobia and Antonio Orlando for technical assistance. The financial support provided by INFN through the projects NAMASSTE and next-NAMASSTE is acknowledged. The position of A.C. was financed through the project NAMASSTE-UNIFI funded by Banca d’Italia and the FIS-ELECOS project funded by MUR. Roberta Sessoli is kindly acknowledged for stimulating scientific discussion. L.T. acknowledges the Deutsche Forschungsgemeinschaft (DFG, German Research Foundation) with the project number 529038510, and Prof. Dr. Sabine Ludwigs for providing access to the photoluminescence spectrometer. A.T. acknowledges that the project was also funded by Next Generation EU Programme: project PRIN-2022JWAF7Y [CUP: B53D23004250006] and I-PHOQS Infrastructure [IR0000016, ID D2B8D520, CUP B53C22001750006].
KeyWords: Induced G Shifts; Paramagnetic-resonance; Basis-sets; Field; Spectra; Ions; Design; Atoms
DOI: 10.1021/jacs.5c10840