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A delocalized arene-bridged diuranium single-molecule magnet

Nature Chemistry volume 3, pages 454–460 (2011)Cite this article

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Abstract

Single-molecule magnets (SMMs) are compounds that, below a blocking temperature, exhibit stable magnetization purely of molecular origin, and not caused by long-range ordering of magnetic moments in the bulk. They thus show promise for applications such as data storage of ultra-high density. The stability of the magnetization increases with increasing ground-state spin and magnetic anisotropy. Transition-metal SMMs typically possess high-spin ground states, but insufficient magnetic anisotropies. Lanthanide SMMs exhibit large magnetic anisotropies, but building high-spin ground states is difficult because they tend to form ionic bonds that limit magnetic exchange coupling. In contrast, the significant covalent bonding and large spin–orbit contributions associated with uranium are particularly attractive for the development of improved SMMs. Here we report a delocalized arene-bridged diuranium SMM. This study demonstrates that arene-bridged polyuranium clusters can exhibit SMM behaviour without relying on the superexchange coupling of spins. This approach may lead to increased blocking temperatures.

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Figure 1: Synthesis and structures of 1–3.
Figure 2: Synthesis and structures of 4 and 5.
Figure 3: Synthesis of 6 and 7.
Figure 4: Ultraviolet/visible/near infrared electronic absorption spectra of 2–7 and [U(I)3(THF)4] in THF solution.
Figure 5: The top six occupied α-spin Kohn–Sham molecular orbitals of 5.
Figure 6: Magnetic data for 5.

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Acknowledgements

We thank the European Research Council, the UK Engineering and Physical Sciences Research Council, the University of Nottingham, the National Nuclear Laboratory and the Marie Curie Intra European Fellowship (F.M.) for support and funding, and the Royal Society for the award of a University Research Fellowship (S.T.L.).

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Authors and Affiliations

  1. School of Chemistry, University of Nottingham, University Park, Nottingham, NG7 2RD, UK

    David P. Mills, Fabrizio Moro, Jonathan McMaster, Joris van Slageren, William Lewis, Alexander J. Blake & Stephen T. Liddle

  2. Institut für Physikalische Chemie, Universität Stuttgart, Pfaffenwaldring 55, Stuttgart, D-70569, Germany

    Joris van Slageren

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Contributions

D.P.M. carried out the synthesis experiments and analysed the characterization data. F.M. and J.v.S. carried out and analysed the magnetic measurements data. J.M. carried out and analysed the DFT calculations. W.L. and A.J.B. carried out the X-ray single-crystal structure analyses. S.T.L. originated the central idea, supervised the work, analysed the data and wrote the manuscript, with contributions from all the co-authors.

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Correspondence to Stephen T. Liddle.

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Supplementary information

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Supplementary information (PDF 1004 kb)

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Crystallographic data for compound 1 (CIF 27 kb)

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Crystallographic data for compound 2 (CIF 41 kb)

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Crystallographic data for compound 3 (CIF 28 kb)

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Crystallographic data for compound 4 (CIF 22 kb)

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Crystallographic data for compound 5 (CIF 33 kb)

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Crystallographic data for compound 6 (CIF 23 kb)

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Crystallographic data for compound 7 (CIF 25 kb)

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Mills, D., Moro, F., McMaster, J. et al. A delocalized arene-bridged diuranium single-molecule magnet. Nature Chem 3, 454–460 (2011). https://doi.org/10.1038/nchem.1028

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