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Strong magneto-chiral dichroism in a paramagnetic molecular helix observed by hard X-rays

Nature Physics volume 11, pages 69–74 (2015)Cite this article

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Abstract

Magneto-chiral dichroism is a non-reciprocal—that is, directional—effect observed in magnetized chiral systems, featuring an unbalanced absorption of unpolarized light depending on the direction of the magnetization. Despite the fundamental interest in a phenomenon breaking both parity and time-reversal symmetries, magneto-chiral dichroism is one of the least investigated aspects of light–matter interaction most likely because of the weakness of the effect in most reported experiments. Here we have exploited the element selectivity of hard X-ray radiation to investigate the magneto-chiral properties of enantiopure crystals of two isostructural molecular helicoidal chains comprising either cobalt(II) or manganese(II) ions. A strong magneto-chiral dichroism, with Kuhn asymmetry of the order of a few per cent, has been observed in the cobalt chains system, whereas it is practically absent for the manganese derivative. The spectral features of the X-ray magneto-chiral dichroism signal differ significantly from the natural and magnetic dichroic contributions and have been rationalized here using the multipolar expansion of matter–radiation interaction.

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Figure 1: Structures of the molecular magnetic helices and experimental set-up.
Figure 2: X-ray absorption and dichroic spectra of the [Co-NIT]∞ helix.
Figure 3: X-ray absorption and dichroic spectra of the [Mn-NIT]∞ helix.
Figure 4: Field dependence of magnetic and magneto-chiral dichroism of the [Co-NIT]∞ helix.

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Acknowledgements

We acknowledge the financial contribution of the European Research Council through the AdG MolNanoMaS (267746). The support of ESRF through beamtime allocation (projects HE-3896 and HC-972) is acknowledged. We are indebted to Y. Joly for assistance in spectra simulation and to R. Caciuffo, Ph. Sainctavit and J. Villain for stimulating discussions.

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Authors and Affiliations

  1. Department of Chemistry ‘Ugo Schiff’ and INSTM Research Unit, University of Florence, 50019 Sesto Fiorentino, Italy

    Roberta Sessoli, Marie-Emmanuelle Boulon, Andrea Caneschi, Matteo Mannini & Lorenzo Poggini

  2. European Synchrotron Radiation Facility (ESRF), 38043 Grenoble, France

    Fabrice Wilhelm & Andrei Rogalev

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  1. Roberta Sessoli
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  2. Marie-Emmanuelle Boulon
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  7. Andrei Rogalev
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Contributions

R.S. and A.R. designed the experiment. A.C. synthesized the materials and grew the crystals. M-E.B. carried out preliminary crystallographic and magnetic analysis. M-E.B., M.M., L.P., R.S., F.W. and A.R. participated in the synchrotron experiments and analysed the data. F.W. simulated the XANES and XNCD spectra. R.S. and A.R. wrote the manuscript with contributions from all authors.

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Correspondence to Roberta Sessoli.

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The authors declare no competing financial interests.

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Sessoli, R., Boulon, ME., Caneschi, A. et al. Strong magneto-chiral dichroism in a paramagnetic molecular helix observed by hard X-rays. Nature Phys 11, 69–74 (2015). https://doi.org/10.1038/nphys3152

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