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Strong exchange and magnetic blocking in N23−-radical-bridged lanthanide complexes

Nature Chemistry volume 3, pages 538–542 (2011)Cite this article

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Abstract

Single-molecule magnets approach the ultimate size limit for spin-based devices. These complexes can retain spin information over long periods of time at low temperature, suggesting possible applications in high-density information storage, quantum computing and spintronics. Notably, the success of most such applications hinges upon raising the inherent molecular spin-inversion barrier. Although recent advances have shown the viability of lanthanide-containing complexes in generating large barriers, weak or non-existent magnetic exchange coupling allows fast relaxation pathways that mitigate the full potential of these species. Here, we show that the diffuse spin of an N23− radical bridge can lead to exceptionally strong magnetic exchange in dinuclear Ln(III) (Ln = Gd, Dy) complexes. The Gd(III) congener exhibits the strongest magnetic coupling yet observed for that ion, while incorporation of the high-anisotropy Dy(III) ion gives rise to a molecule with a record magnetic blocking temperature of 8.3 K at a sweep rate of 0.08 T s−1.

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Figure 1: Structure of the centrosymmetric [{[(Me3Si)2N]2Gd(THF)}2(μ-η2:η2-N2)]− anion, as crystallized in compound 1.
Figure 2: Variable-temperature molar magnetic susceptibility data (χM).
Figure 3: Dynamic magnetic data for 2.
Figure 4: Magnetization (M) versus d.c. magnetic field (H) for 2.

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Acknowledgements

The authors thank the National Science Foundation for support (grant no. CHE-0617063 and CHE-1010002) and T. David Harris for valuable discussions.

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Authors and Affiliations

  1. Department of Chemistry, University of California, Berkeley, 94720-1460, California, USA

    Jeffrey D. Rinehart & Jeffrey R. Long

  2. Department of Chemistry, University of California, Irvine, 92697-2025, California, USA

    Ming Fang & William J. Evans

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  1. Jeffrey D. Rinehart
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  2. Ming Fang
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  3. William J. Evans
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Contributions

W.J.E. and M.F. designed and executed the synthesis and crystallographic characterization of all compounds. J.R.L. and J.D.R. planned and executed the magnetic measurements and analysed the resulting data. All authors were involved in the writing of the manuscript.

Corresponding authors

Correspondence to William J. Evans or Jeffrey R. Long.

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The authors declare no competing financial interests.

Supplementary information

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Supplementary information (PDF 1282 kb)

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Crystallographic data for compound 1 (CIF 24 kb)

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Crystallographic data for compound 2 (CIF 21 kb)

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Rinehart, J., Fang, M., Evans, W. et al. Strong exchange and magnetic blocking in N23−-radical-bridged lanthanide complexes. Nature Chem 3, 538–542 (2011). https://doi.org/10.1038/nchem.1063

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