Skip to main content

Thank you for visiting nature.com. You are using a browser version with limited support for CSS. To obtain the best experience, we recommend you use a more up to date browser (or turn off compatibility mode in Internet Explorer). In the meantime, to ensure continued support, we are displaying the site without styles and JavaScript.

  • Letter
  • Published:

High-temperature metal–organic magnets

Nature volume 445, pages 291–294 (2007)Cite this article

Abstract

For over two decades there have been intense efforts aimed at the development of alternatives to conventional magnets, particularly materials comprised in part or wholly of molecular components1,2. Such alternatives offer the prospect of realizing magnets fabricated through controlled, low-temperature, solution-based chemistry, as opposed to high-temperature metallurgical routes, and also the possibility of tuning magnetic properties through synthesis. However, examples of magnetically ordered molecular materials at or near room temperature are extremely rare3, and the properties of these materials are often capricious and difficult to reproduce. Here we present a versatile solution-based route to a new class of metal–organic materials exhibiting magnetic order well above room temperature. Reactions of the metal (M) precursor complex bis(1,5-cyclooctadiene)nickel with three different organics A—TCNE (tetracyanoethylene), TCNQ (7,7,8,8-tetracyanoquinodimethane) or DDQ (2,3-dichloro-5,6-dicyano-1,4-benzoquinone)—proceed via electron transfer from nickel to A and lead to materials containing Ni(II) ions and reduced forms of A in a 2:1 Ni:A ratio—that is, opposite to that of conventional (low Curie temperature) MA2-type magnets. These materials also contain oxygen-based species within their architectures. Magnetic characterization of the three compounds reveals spontaneous field-dependent magnetization and hysteresis at room temperature, with ordering temperatures well above ambient. The unusual stoichiometry and striking magnetic properties highlight these three compounds as members of a class of stable magnets that are at the interface between conventional inorganic magnets and genuine molecule-based magnets.

This is a preview of subscription content, access via your institution

Access options

Buy this article

  • Purchase on Springer Link
  • Instant access to full article PDF
Buy now

Prices may be subject to local taxes which are calculated during checkout

Figure 1: Temperature dependence of field-cooled (25 Oe) magnetization for 1–3.
Figure 2: Magnetic hysteresis loops for 1 (black line), 2 (blue line), and 3 (red line) at 300 K.
Figure 3: Temperature dependence of the a.c. susceptibility of 3 at different frequencies.

Similar content being viewed by others

References

  1. Kahn, O. Molecular Magnetism (VCH, New York, 1993)

    Google Scholar 

  2. Miller, J. S. Organometallic- and organic-based magnets: New chemistry and new materials for the new millennium. Inorg. Chem. 39, 4392–4408 (2000)

    Article  CAS  Google Scholar 

  3. Miller, J. S. & Epstein, A. J. Molecule-based magnets—an overview. MRS Bull. 25, 21–28 (2000)

    Article  CAS  Google Scholar 

  4. Ferlay, S., Mallah, T., Ouahes, R., Veillet, P. & Verdaguer, M. A room-temperature organometallic magnet based on Prussian blue. Nature 378, 701–703 (1995)

    Article  ADS  CAS  Google Scholar 

  5. Manriquez, J. M., Yee, G. T., McLean, R. S., Epstein, A. J. & Miller, J. S. A room temperature molecular/organic based magnet. Science 252, 1415–1417 (1991)

    Article  ADS  CAS  Google Scholar 

  6. Miller, J. S. & Epstein, A. J. Tetracyanoethylene-based organic magnets. Chem. Commun. 1319–1325 (1998)

  7. Fitzgerald, J. P., Kaul, B. B. & Yee, G. T. Vanadium [dicyanoperfluorostilbene]2⋅yTHF: a molecule-based magnet with TC ≈ 205 K. Chem. Commun.49–50 (2000)

  8. Vickers, E. B., Selby, T. D. & Miller, J. S. Magnetically ordered (TC=200 K) bis(tetracyanopyrazine)vanadium, V[TCNP]2⋅yCH2Cl2 . J. Am. Chem. Soc. 126, 3716–3717 (2004)

    Article  CAS  Google Scholar 

  9. Zhang, J. et al. [M-II(tcne)2].xCH2Cl2 (M=Mn, Fe, Co, Ni): molecule-based magnets with TC values above 100K and coercive fields up to 6500Oe. Angew. Chem. Int. Edn Engl. 37, 657–660 (1998)

    Article  CAS  Google Scholar 

  10. Pokhodnya, K. I., Petersen, N. & Miller, J. S. Iron pentacarbonyl as a precursor for molecule-based magnets: Formation of Fe[TCNE]2 (TC=100 K) and Fe[TCNQ]2 (TC=35 K) magnets. Inorg. Chem. 41, 1996–1997 (2002)

    Article  CAS  Google Scholar 

  11. Vickers, E. B., Senesi, A. & Miller, J. S. Ni[TCNE]2⋅zCH2Cl2 (TC=13 K) and VxNi1-x[TCNE]y⋅zCH2Cl2 solid solution room temperature magnets. Inorg. Chim. Acta 357, 3889–3894 (2004)

    Article  CAS  Google Scholar 

  12. Kathirgamanathan, P. & Rosseinsku, D. R. Electrocrystallized metal-tetracyanoquinodimethane salts with high electrical conductivity. J. Chem. Soc. Chem. Commun.840–841 (1980)

  13. Ferraro, J. R. & Williams, J. M. Introduction to Synthetic Electrical Conductors (Academic Press, New York, 1987)

    Google Scholar 

  14. Clerac, R. et al. Glassy magnets composed of metals coordinated to 7,7,8,8-tetracyanoquinodimethane: M(TCNQ)2 (M = Mn, Fe, Co, Ni). Chem. Mater. 15, 1840–1850 (2003)

    Article  CAS  Google Scholar 

  15. Long, G. & Willett, R. D. Electrochemical synthesis, characterization and magnetic studies of Ni/TCNQ salts. Inorg. Chim. Acta 313, 1–14 (2001)

    Article  CAS  Google Scholar 

  16. Osan, J. et al. Evaluation of energy-dispersive x-ray spectra of low-Z elements from electron-probe microanalysis of individual particles. X-ray Spectrom. 30, 419–426 (2001)

    Article  ADS  CAS  Google Scholar 

  17. Kaim, W. & Moscherosch, M. The coordination chemistry of TCNE, TCNQ, and related polynitrile pi-acceptors. Coord. Chem. Rev. 129, 157–193 (1994)

    Article  CAS  Google Scholar 

  18. Miller, J. S. & Dixon, D. A. Dianion stabilization by M(C5(CH3)5)2)+—theoretical evidence for a localized ring in (DDQ)2-. Science 235, 871–873 (1987)

    Article  ADS  CAS  Google Scholar 

  19. Murphy, V. J. & O’Hare, D. Synthesis and magnetic characterization of Fe(η5-C9Me7)2⋅+A•- (A = TCNE, TCNQ, DDQ)—X-ray structure of Fe(η5-C9Me7)2⋅+TCNQ•-. Inorg. Chem. 33, 1833–1841 (1994)

    Article  CAS  Google Scholar 

  20. Miller, J. S. et al. Radical ion salts of 2,3-dichloro-5,6-dicyanobenzoquinone and metallocenes—a reexamination of their magnetic and spectroscopic properties. J. Am. Chem. Soc. 108, 4459–4466 (1986)

    Article  CAS  Google Scholar 

  21. Vickers, E. B., Giles, I. D. & Miller, J. S. M[TCNQ]x-based magnets (M = Mn, Fe, Co, Ni; TCNQ=7,7,8,8-tetracyano-p-quinodimethane). Chem. Mater. 17, 1667–1672 (2005)

    Article  CAS  Google Scholar 

  22. Bell, S. E. et al. Novel and stable metal-metal-bonded diruthenium(I) complexes containing TCNX0/•- in both the inner and the outer coordination sphere (TCNX = TCNE, TCNQ)—a combined EPR/ENDOR spectroscopic, UV/vis/near-IR spectroscopic, and IR spectroscopic and electrochemical investigation. Inorg. Chem. 31, 3269–3276 (1992)

    Article  CAS  Google Scholar 

  23. Yang, D. Q. & Sacher, E. Interaction of evaporated nickel nanoparticles with highly oriented pyrolytic graphite: Back-bonding to surface defects, as studied by x-ray photoelectron spectroscopy. J. Phys. Chem. B 109, 19329–19334 (2005)

    Article  CAS  Google Scholar 

  24. Buschmann, W. E., Ensling, J., Gütlich, P. & Miller, J. S. Electron transfer, linkage isomerization, bulk magnetic order, and spin-glass behavior in the iron hexacyanomanganate Prussian blue analogue. Chem. Eur. J. 5, 3019–3028 (1999)

    Article  CAS  Google Scholar 

  25. Pokhodnya, V. I., Pejakovic, D., Epstein, A. J. & Miller, J. S. Effect of solvent on the magnetic properties of the high-temperature V[TCNE]x molecule-based magnet. Phys. Rev. B 63, 174408 (2001)

    Article  ADS  Google Scholar 

  26. Schrauzer, G. N. & Thyret, H. Novel “sandwich” compounds of nickel(0); duroquinone-nickel(0) complexes with cyclic dienes. Z. Naturforsch. 17b, 73–76 (1962)

    Article  CAS  Google Scholar 

  27. Leslie-Pelecky, D. L. & Rieke, R. D. Magnetic properties of nanostructured materials. Chem. Mater. 8, 1770–1783 (1996)

    Article  CAS  Google Scholar 

  28. Koltypin, Y. et al. Encapsulation of nickel nanoparticles in carbon obtained by the sonochemical decomposition of Ni(C8H12)2 . Chem. Mater. 11, 1331–1335 (1999)

    Article  CAS  Google Scholar 

  29. Cordente, N. et al. Synthesis and magnetic properties of nickel nanorods. Nano Lett. 10, 565–568 (2001)

    Article  ADS  Google Scholar 

  30. Khadar, M. A., Biju, V. & Inoue, A. Effect of finite size on the magnetization behavior of nanostructured nickel oxide. Mater. Res. Bull. 38, 1341–1349 (2003)

    Article  CAS  Google Scholar 

Download references

Acknowledgements

We thank the Natural Sciences and Engineering Research Council of Canada and the University of Victoria for support of this research. We thank F. Palacio (Zaragoza) for assistance with some magnetic measurements and B. Gowen (Victoria) for assistance in scanning TEM and EDX measurements.

Author Contributions R.J. and R.G.H contributed equally to this work. R.J. initiated the work under the supervision of R.G.H. R.J. performed all the syntheses, control experiments, characterization, SEM and EDX measurements of the magnets. K.K. attempted to crystallize these materials, assisted in some control experiments and also processed the magnetic, X-ray photoelectron spectroscopic data. J.B.G. performed some magnetic measurements. K.A.R.M. and K.W. conducted the X-ray photoelectron spectroscopic studies. R.J. and R.G.H. wrote the manuscript. All authors have discussed the results presented and commented on the paper.

Author information

Authors and Affiliations

  1. Department of Chemistry, University of Victoria, PO Box 3065 STN CSC, British Columbia, V8W 3V6, Victoria, Canada

    Rajsapan Jain, Khayrul Kabir, Joe B. Gilroy & Robin G. Hicks

  2. Department of Chemistry, University of British Columbia, British Columbia, V6T 1Z1, Vancouver, Canada

    Keith A. R. Mitchell & Kin-chung Wong

Authors
  1. Rajsapan Jain
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Khayrul Kabir
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Joe B. Gilroy
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Keith A. R. Mitchell
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Kin-chung Wong
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Robin G. Hicks
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Robin G. Hicks.

Ethics declarations

Competing interests

Reprints and permissions information is available at www.nature.com/reprints. The authors declare no competing financial interests.

Supplementary information

Supplementary Information

This file contains Supplementary Methods; Supplementary Data and Supplementary Figures 1-10 with legends. This file contains descriptions of materials & techniques; compositional analyses data; and spectroscropic data (infrared spectra, 3 figures; solid state electronic spectra, 4 figures; XPS spectra, 6 figures; magnetic data, 13 figures; SEM images, 3 figures; EDX images and spectra, 9 figures; TEM images, 3 figures). (PDF 2229 kb)

Rights and permissions

Reprints and permissions

About this article

Cite this article

Jain, R., Kabir, K., Gilroy, J. et al. High-temperature metal–organic magnets. Nature 445, 291–294 (2007). https://doi.org/10.1038/nature05439

Download citation

  • Received:

  • Accepted:

  • Issue Date:

  • DOI: https://doi.org/10.1038/nature05439

This article is cited by

Comments

By submitting a comment you agree to abide by our Terms and Community Guidelines. If you find something abusive or that does not comply with our terms or guidelines please flag it as inappropriate.

Search

Advanced search

Quick links

Nature Briefing

Sign up for the Nature Briefing newsletter — what matters in science, free to your inbox daily.

Get the most important science stories of the day, free in your inbox. Sign up for Nature Briefing