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Molecular magnetic hysteresis at 60 kelvin in dysprosocenium

Nature volume 548, pages 439–442 (2017)Cite this article

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Abstract

Lanthanides have been investigated extensively for potential applications in quantum information processing and high-density data storage at the molecular and atomic scale. Experimental achievements include reading and manipulating single nuclear spins1,2, exploiting atomic clock transitions for robust qubits3 and, most recently, magnetic data storage in single atoms4,5. Single-molecule magnets exhibit magnetic hysteresis of molecular origin6—a magnetic memory effect and a prerequisite of data storage—and so far lanthanide examples have exhibited this phenomenon at the highest temperatures. However, in the nearly 25 years since the discovery of single-molecule magnets7, hysteresis temperatures have increased from 4 kelvin to only about 14 kelvin8,9,10 using a consistent magnetic field sweep rate of about 20 oersted per second, although higher temperatures have been achieved by using very fast sweep rates11,12 (for example, 30 kelvin with 200 oersted per second)12. Here we report a hexa-tert-butyldysprosocenium complex—[Dy(Cpttt)2][B(C6F5)4], with Cpttt = {C5H2tBu3-1,2,4} and tBu = C(CH3)3—which exhibits magnetic hysteresis at temperatures of up to 60 kelvin at a sweep rate of 22 oersted per second. We observe a clear change in the relaxation dynamics at this temperature, which persists in magnetically diluted samples, suggesting that the origin of the hysteresis is the localized metal–ligand vibrational modes that are unique to dysprosocenium. Ab initio calculations of spin dynamics demonstrate that magnetic relaxation at high temperatures is due to local molecular vibrations. These results indicate that, with judicious molecular design, magnetic data storage in single molecules at temperatures above liquid nitrogen should be possible.

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Figure 1: Synthesis and structure of [Dy(Cpttt)2][B(C6F5)4] (1).
Figure 2: Magnetic hysteresis of 1.
Figure 3: Relaxation dynamics of 1.
Figure 4: Ab initio spin dynamics.

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Acknowledgements

We acknowledge funding from the Engineering and Physical Sciences Research Council (studentship to C.A.P.G. and EP/P002560/1 for F.O. and D.R.), the Ramsay Memorial Fellowships Trust (fellowship to N.F.C.) and the University of Manchester. We thank the University of Manchester for access to the SQUID magnetometer and Computational Shared Facility and R. E. P. Winpenny, E. J. L. McInnes and D. Collison for comments.

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  1. School of Chemistry, The University of Manchester, Oxford Road, Manchester, M13 9PL, UK

    Conrad A. P. Goodwin, Fabrizio Ortu, Daniel Reta, Nicholas F. Chilton & David P. Mills

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  1. Conrad A. P. Goodwin
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Contributions

C.A.P.G. and D.P.M. provided the original concept. C.A.P.G. synthesized and characterized the compounds. F.O. carried out the single-crystal X-ray diffraction analysis and supporting synthetic/characterization work. N.F.C. collected and interpreted magnetic data. N.F.C. devised the relaxation dynamics model and wrote computer programs to perform these calculations. D.R. and N.F.C. performed the calculations. D.P.M. and N.F.C. wrote the manuscript with contributions from all authors. D.P.M. and N.F.C. supervised the project.

Corresponding authors

Correspondence to Nicholas F. Chilton or David P. Mills.

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The authors declare no competing financial interests.

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Reviewer Information Nature thanks R. Sessoli, P. Zhang and the other anonymous reviewer(s) for their contribution to the peer review of this work.

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Supplementary information

Supplementary Information

This file contains Supplementary Methods, Discussion, Data and Equations, Supplementary Tables 1-21, Supplementary Figures 1-64. It includes details of synthesis methods, crystallography, NMR, UV-Vis-NIR, vibrational spectra, magnetic data, theoretical analysis and additional references. This file was replaced on 4 September 2017 to correct a file corruption in the equations. (PDF 26419 kb)

Supplementary Data

Crystallographic Information File for 1 and 5-7. (CIF 4576 kb)

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Goodwin, C., Ortu, F., Reta, D. et al. Molecular magnetic hysteresis at 60 kelvin in dysprosocenium. Nature 548, 439–442 (2017). https://doi.org/10.1038/nature23447

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