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Formation of the layered conductive magnet CrCl2(pyrazine)2 through redox-active coordination chemistry

Nature Chemistry volume 10, pages 1056–1061 (2018)Cite this article

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Abstract

The unique properties of graphene, transition-metal dichalcogenides and other two-dimensional (2D) materials have boosted interest in layered coordination solids. In particular, 2D materials that behave as both conductors and magnets could find applications in quantum magnetoelectronics and spintronics. Here, we report the synthesis of CrCl2(pyrazine)2, an air-stable layered solid, by reaction of CrCl2 with pyrazine (pyz). This compound displays a ferrimagnetic order below ∼55 K, reflecting the presence of strong magnetic interactions. Electrical conductivity measurements demonstrate that CrCl2(pyz)2 reaches a conductivity of 32 mS cm–1 at room temperature, which operates through a 2D hopping-based transport mechanism. These properties are induced by the redox-activity of the pyrazine ligand, which leads to a smearing of the Cr 3d and pyrazine π states. We suggest that the combination of redox-active ligands and reducing paramagnetic metal ions represents a general approach towards tuneable 2D materials that consist of charge-neutral layers and exhibit both long-range magnetic order and high electronic conductivity.

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Fig. 1: Structure of CrCl2(pyz)2.
Fig. 2: XAS at the pre-K-edge region.
Fig. 3: Magnetic properties for CrCl2(pyz)2.
Fig. 4: DFT calculations.
Fig. 5: XMCD at the Cr K-edge.
Fig. 6: Electrical conductivity.

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Data availability

All data generated and analysed in this study are included in the Article and its Supplementary Information, and are also available from the authors upon request. Crystallographic information has been deposited in the Cambridge Crystallographic Data Centre under accession codes CCDC 1563526 (CrCl2(pyz)2) and CCDC 1563527 (Cr(iii)).

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Acknowledgements

K.S.P. thanks the VILLUM Foundation for a VILLUM Young Investigator grant (15374). K.S.P. and R.C. thank the Danish Research Council for Independent Research for a DFF-Sapere Aude Research Talent grant (4090-00201), the University of Bordeaux, the Région Aquitaine, the CNRS, the GdR MCM-2: Magnétisme et Commutation Moléculaires and the MOLSPIN COST action CA15128. M.L.A. and J.R.L. thank the National Science Foundation (grant DMR-1611525) for funding support. K.B. is thankful for funding by the Danish National Research Foundation (Center for Materials Crystallography, DNRF93). D.N.W. thanks the Diamond Light Source Ltd for beam time (I11; EE13284). Theory and computation were supported by the US Department of Energy, Office of Science, Office of Basic Energy Sciences (Theory FWP) Materials Sciences and Engineering Division (DE-AC02-05CH11231). R.C. and J.R.L. are grateful to the France-Berkeley Fund and the CNRS for PICS no. 06485. Work at the Molecular Foundry was supported by the Office of Science, Office of Basic Energy Sciences, of the US Department of Energy under contract no. DE-AC02-05CH11231. J. Bendix, E. Suturina, B. B. Iversen, L. E. Darago, F. Hof, T. Maris and E. Lebraud are thanked for experimental assistance and helpful discussions.

Author information

Author notes

  1. Dumitru Samohvalov

    Present address: Sara Pharm Solutions, Bucharest, Romania

Authors and Affiliations

  1. CNRS, CRPP, UMR 5031, Pessac, France

    Kasper S. Pedersen, Panagiota Perlepe, Mathieu Rouzières, Dumitru Samohvalov & Rodolphe Clérac

  2. Univ. Bordeaux, CRPP, UMR 5031, Pessac, France

    Kasper S. Pedersen, Panagiota Perlepe, Mathieu Rouzières, Dumitru Samohvalov & Rodolphe Clérac

  3. Department of Chemistry, Technical University of Denmark, Lyngby, Denmark

    Kasper S. Pedersen & Laura Voigt

  4. CNRS, ICMCB, UMR 5026, Pessac, France

    Panagiota Perlepe

  5. Univ. Bordeaux, ICMCB, UMR 5026, Pessac, France

    Panagiota Perlepe

  6. Department of Chemistry, University of California Berkeley, Berkeley, CA, USA

    Michael L. Aubrey & Jeffrey R. Long

  7. Department of Chemistry, University of Oxford, Oxford, UK

    Daniel N. Woodruff

  8. Molecular Foundry, Lawrence Berkeley National Laboratory, Berkeley, CA, USA

    Sebastian E. Reyes-Lillo & Jeffrey B. Neaton

  9. Department of Physics, University of California Berkeley, Berkeley, CA, USA

    Sebastian E. Reyes-Lillo & Jeffrey B. Neaton

  10. Departamento de Ciencias Físicas, Universidad Andres Bello, Santiago, Chile

    Sebastian E. Reyes-Lillo

  11. Department of Chemistry, University of Copenhagen, Copenhagen, Denmark

    Anders Reinholdt

  12. Department of Physics and Astronomy – Centre for Storage Ring Facilities (ISA), Aarhus University, Aarhus, Denmark

    Zheshen Li

  13. Center for Materials Crystallography, Department of Chemistry and iNano, Aarhus, Denmark

    Kasper Borup

  14. ESRF – The European Synchrotron, Grenoble, France

    Fabrice Wilhelm & Andrei Rogalev

  15. Kavli Energy Nanosciences Institute at Berkeley, Berkeley, CA, USA

    Jeffrey B. Neaton

  16. Department of Chemical and Biomolecular Engineering, University of California Berkeley, Berkeley, CA, USA

    Jeffrey R. Long

  17. Materials Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, CA, USA

    Jeffrey R. Long

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Contributions

K.S.P. and R.C. conceived, planned and designed the research project. K.S.P., P.P., D.W., A.R. and D.S. executed the syntheses and the chemical and crystallographic analyses. L.V. obtained and analysed the scanning electron microscopy data. M.L.A., M.R., P.P., J.R.L. and R.C. performed and analysed the electrical conductivity experiments. M.R., K.S.P. and R.C. performed and analysed the magnetic susceptibility measurements. Z.L. and K.S.P. obtained and analysed the UPS and NIR–IR data. K.B. and K.S.P. obtained and analysed the Seebeck measurements. S.E.R.-L., J.N. and K.S.P. performed the DFT studies. F.W., A.R., K.S.P., P.P. and R.C. executed the X-ray spectroscopy experiments and analysed the results. All coauthors were involved in the writing of the manuscript and they have all given their consent to its publication.

Corresponding authors

Correspondence to Kasper S. Pedersen or Rodolphe Clérac.

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Supplementary information

Supplementary Information

Additional experimental and computation details; structural, magnetic, electronic, spectroscopic and computational data; Supplementary Figures 1–15; Supplementary Table 1 and Supplementary References 1–23

Crystallographic data

CIF for compound CrCl2(pyz)2; CCDC reference: 1563526

Crystallographic data

CIF for compound Cr(iii); CCDC reference: 1563527

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Pedersen, K.S., Perlepe, P., Aubrey, M.L. et al. Formation of the layered conductive magnet CrCl2(pyrazine)2 through redox-active coordination chemistry. Nature Chem 10, 1056–1061 (2018). https://doi.org/10.1038/s41557-018-0107-7

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