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Uranium and manganese assembled in a wheel-shaped nanoscale single-molecule magnet with high spin-reversal barrier

Nature Chemistry volume 4, pages 1011–1017 (2012)Cite this article

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Abstract

Discrete molecular compounds that exhibit both magnetization hysteresis and slow magnetic relaxation below a characteristic ‘blocking’ temperature are known as single-molecule magnets. These are promising for applications including memory devices and quantum computing, but require higher spin-inversion barriers and hysteresis temperatures than currently achieved. After twenty years of research confined to the d- block transition metals, scientists are moving to the f-block to generate these properties. We have now prepared, by cation-promoted self-assembly, a large 5f–3d U12Mn6 cluster that adopts a wheel topology and exhibits single-molecule magnet behaviour. This uranium-based molecular wheel shows an open magnetic hysteresis loop at low temperature, with a non-zero coercive field (below 4 K) and quantum tunnelling steps (below 2.5 K), which suggests that uranium might indeed provide a route to magnetic storage devices. This molecule also represents an interesting model for actinide nanoparticles occurring in the environment and in spent fuel separation cycles.

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Figure 1: Reaction scheme.
Figure 2: Solid-state structure of {[UO2(salen)]4Ca2} (1) and [{[UO2(salen)]2Mn(Py)3}6] (2).
Figure 3: Temperature dependence of the molar d.c. magnetic susceptibility χM(T) of complex 2.
Figure 4: Low-temperature magnetic hysteresis loops showing an open cycle.
Figure 5: Dynamic magnetic data and magnetization relaxation time data for compound 2.

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Acknowledgements

The authors acknowledge support from the Commissariat à l'Energie Atomique, Direction de l'Energie Nucléaire, RBPCH programme and by the ‘Agence Nationale de la Recherche’, (ANR-10-BLAN-0729). The authors also thank F. Jacquot and L. Dubois for support and suggestions regarding the magnetic measurements, A. De Geyer for recording the PXRD diffractogram, N. Magnani, P. Santini and S. Carretta for useful discussions on the interpretation of the magnetic data.

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  1. Laboratoire de Reconnaissance Ionique et Chimie de Coordination, SCIB, UMR-E 3 CEA-UJF, INAC, CEA-Grenoble, 17 rue des Martyrs, F-38054, Grenoble Cedex 09, France

    Victor Mougel, Lucile Chatelain, Jacques Pécaut & Marinella Mazzanti

  2. European Commission, Joint Research Centre, Institute for Transuranium Elements, PO Box 2340, D-76125, Karlsruhe, Germany

    Roberto Caciuffo, Eric Colineau & Jean-Christophe Griveau

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  1. Victor Mougel
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Contributions

V.M. carried out the synthesis experiments, measured the d.c. magnetic data and analysed the experimental data. L.C. performed the preliminary experiments. R.C., E.C. and J.C.G. collected and analysed the magnetic measurement data and created the magnetic model. J.P. and V.M. carried out X-ray single-crystal structure analyses. M.M. originated the central idea, coordinated the work and analysed the experimental data. M.M., V.M. and R.C. wrote the manuscript.

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Correspondence to Marinella Mazzanti.

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Supplementary information

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Supplementary information (PDF 1796 kb)

Supplementary information

Crystallographic data for {[UO2(salen)]4Ca2}, complex 1 (CIF 26 kb)

Supplementary information

Crystallographic data for [{[UO2(salen)]2Mn(Py)3}6], complex 2 (CIF 61 kb)

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Mougel, V., Chatelain, L., Pécaut, J. et al. Uranium and manganese assembled in a wheel-shaped nanoscale single-molecule magnet with high spin-reversal barrier. Nature Chem 4, 1011–1017 (2012). https://doi.org/10.1038/nchem.1494

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