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Magnetic relaxation pathways in lanthanide single-molecule magnets

Nature Chemistry volume 5, pages 673–678 (2013)Cite this article

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Abstract

Single-molecule magnets are compounds that exhibit magnetic bistability caused by an energy barrier for the reversal of magnetization (relaxation). Lanthanide compounds are proving promising as single-molecule magnets: recent studies show that terbium phthalocyanine complexes possess large energy barriers, and dysprosium and terbium complexes bridged by an N23− radical ligand exhibit magnetic hysteresis up to 13 K. Magnetic relaxation is typically controlled by single-ion factors rather than magnetic exchange (whether one or more 4f ions are present) and proceeds through thermal relaxation of the lowest excited states. Here we report polylanthanide alkoxide cage complexes, and their doped diamagnetic yttrium analogues, in which competing relaxation pathways are observed and relaxation through the first excited state can be quenched. This leads to energy barriers for relaxation of magnetization that exceed 800 K. We investigated the factors at the lanthanide sites that govern this behaviour.

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Figure 1: The structure of [Dy4K2O(OtBu)12] (3); compounds 1–5 are isostructural.
Figure 2: Magnetic measurements on {Dy4K2} (3) and Dy in {Y4K2} Dy@7.
Figure 3: Low-lying electronic structure for 3 and 6.
Figure 4: Single-crystal measurements of M(H) measured on a micro-SQUID array.

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Acknowledgements

This work was supported by the Engineering and Physical Sciences Research Council (UK), by the Flemish Science Foundation (fellowship to L.U.) and by the European Research Council Advanced Grant MolNanoSpin (number 226558) and ICT-2007.8.0 Future Emerging Technologies Open, Quantum Information Processing Specific Targeted Research Project number 211284 MolSpinQIP. R.E.P.W. thanks The Royal Society for a Wolfson research merit award, and financial support from the Institute for Nanoscale Physics and Chemistry and Methusalem programs at KU Leuven is gratefully acknowledged. We also acknowledge Diamond Light Source for access to synchrotron X-radiation.

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Authors and Affiliations

  1. School of Chemistry and Photon Science Institute, The University of Manchester, Oxford Road, Manchester, M13 9PL, UK

    Robin J. Blagg, Floriana Tuna, James Speak, Priyanka Comar, David Collison, Eric J. L. McInnes & Richard E. P. Winpenny

  2. Division of Quantum and Physical Chemistry, Katholieke Universiteit Leuven, Celestijenlaan 200F, Leuven, 3001, Belgium

    Liviu Ungur & Liviu F. Chibotaru

  3. Institut Néel, Centre National de la Recherche and Université Joseph Fourier, BP 166, Grenoble Cedex 9, 38042, France

    Wolfgang Wernsdorfer

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Contributions

E.J.L.M., D.C. and R.E.P.W. designed the research. R.J.B., P.C. and J.S. made the compounds; R.J.B. also carried out the X-ray studies. L.U. and L.F.C. performed the ab initio calculations and proposed the interpretation. F.T. and W.W. performed the magnetic measurements. E.J.L.M., D.C. and R.E.P.W. co-wrote the paper with input from all other authors.

Corresponding authors

Correspondence to Eric J. L. McInnes, Liviu F. Chibotaru or Richard E. P. Winpenny.

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The authors declare no competing financial interests.

Supplementary information

Supplementary information

Supplementary information (PDF 3719 kb)

Supplementary information

Crystallographic data for compound 1.C6H14, [Gd4K2O(OtBu)12].C6H14 (CIF 106 kb)

Supplementary information

Crystallographic data for compound 2.C6H14, [Tb4K2O(OtBu)12].C6H14 (CIF 106 kb)

Supplementary information

Crystallographic data for compound 3.C6H14, [Dy4K2O(OtBu)12].C6H14 (CIF 113 kb)

Supplementary information

Crystallographic data for compound 4.C6H14, [Ho4K2O(OtBu)12].C6H14 (CIF 106 kb)

Supplementary information

Crystallographic data for compound 5.C6H14, [Er4K2O(OtBu)12].C6H14 (CIF 110 kb)

Supplementary information

Crystallographic data for compound 7.C6H14, [Y4K2O(OtBu)12].C6H14 (CIF 107 kb)

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Blagg, R., Ungur, L., Tuna, F. et al. Magnetic relaxation pathways in lanthanide single-molecule magnets. Nature Chem 5, 673–678 (2013). https://doi.org/10.1038/nchem.1707

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