Skip to main content
SpringerLink
Log in

Density functional theory study of the magnetic properties of rare earth complexes: the magnetic coupling mechanism in YIII and GdIII complexes with nitronyl nitroxide

  • Published:
Science in China Series B: Chemistry Aims and scope Submit manuscript

Abstract

The magnetic coupling interactions of the nitronyl nitroxide radicals bound to diamagnetic (YIII) and paramagnetic (GdIII) rare earth ions in two model magnetic systems based on novel rare earth organic radical complexes Ln(hfac)3(NITPhOCH3)2 (Ln = YIII 1, GdIII 2; hafc = hexafluoroacetylacetonate; NITPhOCH3 = 4′-methoxyo-phenyl-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide) have been investigated by density functional theory (DFT). The magnetic coupling mechanisms were also explored from the viewpoint of molecular orbital and spin density populations. DFT calculations show that the empty 4d-orbitals of YIII and 5d-orbitals of GdIII play an important role in the antiferromagnetic coupling between the two nitronyl nitroxide radical ligands, and that the ferromagnetic coupling between the GdIII ion and the radical magnetic centers can be attributed to the nearly complete localization of the isotropic 4f-shell and singly occupied magnetic orbital (Π*) of the nitronyl nitroxide.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Similar content being viewed by others

References

  1. Kahn M, Sutter J P, Golhen S, Guionneau P, Ouahab L, Kahn O, Chasseau D. Systematic investigation of the nature of the coupling between a Ln(III) ion (Ln = Ce(III) to Dy(III)) and its aminoxyl radical ligands. structural and magnetic characteristics of a series of {Ln(organic radical)2} compounds and the related {Ln(nitrone)2} derivatives. J Am Chem Soc, 2000, 122: 3413–3421

    Article  CAS  Google Scholar 

  2. Sutter J P, Kahn M, Golhen S, Ouahab L, Kahn O. Synthesis and magnetic behavior of rare-earth complexes with N,O-chelating nitronyl nitroxide triazole ligands: example of a [Gd-III{organic radical}2] compound with an S=9/2 ground state. Chem Eur J, 1998, 4: 571–576

    Article  CAS  Google Scholar 

  3. Lescop C, Luneau D, Belorizky E, Fries P, Guillot M, Rey P. Unprecedented antiferromagnetic metal-ligand interactions in gadolinium-nitroxide derivatives. Inorg Chem, 1999, 38: 5472–5473

    Article  CAS  Google Scholar 

  4. Sanada T, Suzuki T, Yoshida T, Kaizaki S. Heterodinuclear complexes containing d- and f-block elements: synthesis, structural characterization, and metal-metal interactions of novel chromium(III)-lanthanide(III) compounds bridged by oxalate. Inorg Chem, 1998, 37: 4712–4717

    Article  CAS  Google Scholar 

  5. Benelli C, Caneschi A, Gatteschi D, Laugier J, Rey P. Structure and magnetic properties of a gadolinium hexafluoroacetylacetonate adduct with the radical 4, 4, 5, 5-tetramethyl-2-phenyl-4,5-dihydro-1H-imidazolyl-3-oxide-1-oxyl. Angew Chem Int Ed Engl, 1987, 26: 913–915

    Article  Google Scholar 

  6. Benelli C, Caneschi A, Gatteschi D, Pardi L, Rey P. Linear-chain gadolinium(III) nitronyl nitroxide complexes with dominant next-nearest-neighbor magnetic interactions. Inorg Chem, 1990, 29: 4223–4228

    Article  CAS  Google Scholar 

  7. Benelli C, Caneschi A, Gatteschi D, Pardi L. Gadolinium(III) com plexes with pyridine-substituted nitronyl nitroxide radicals. Inorg Chem, 1992, 31: 741–746

    Article  CAS  Google Scholar 

  8. Pontillon Y, Caneschi A, Gatteschi D, Grand A, Ressouche E, Sessoli R, Schweizer J. Experimental spin density in a purely organic free radical: visualisation of the ferromagnetic exchange pathway in p-(methylthio)phenyl nitronyl nitroxide, NIT(Sme)Ph. Chem Eur J, 1999, 5: 3616–3624

    Article  CAS  Google Scholar 

  9. Ressouche E, Boucherle J X, Gillon B, Rey P, Schweizer J. Spin density maps in nitroxide-copper(II) complexes. A polarized neutron diffraction determination. J Am Chem Soc, 1993, 115: 3610–3617

    Article  CAS  Google Scholar 

  10. Zhang L, Chen Z D. Magnetic exchange interaction in the μ-hydroxo bridged vanadium(IV) dimers: a density functional theory combined with broken-symmetry approach. Chem Phys Lett, 2001, 345: 353–360

    Article  CAS  Google Scholar 

  11. Ren Q H, Chen Z D, Ren J, Wei H Y, Feng W T, Zhang L. Ferromagnetic coupling behavior in oxo-bridged binuclear bis(η5-cyclopentadienyl)titanium(III) complex (Cp2Ti)2(μ-O): a density functional theory combined with broken-symmetry approach. J Phys Chem A, 2002, 106: 6161–6166

    Article  CAS  Google Scholar 

  12. Ren Q H, Chen Z D, Zhang L. Magnetic exchange cooperative effect of the bridges in μ-hydroxo and μ-acetato bridged chromium(III) dimers: a density functional theory coupling the broken-symmetry approach. Chem Phys Lett, 2002, 364: 475–483

    Article  CAS  Google Scholar 

  13. Chen Z D, Xu Z T, Zhang L, Yan F, Lin Z Y. Magnetic exchange interactions in oxo-bridged diiron(III) systems: density functional calculations coupling the broken symmetry approach. J Phys Chem A, 2001, 105: 9710–9716

    Article  CAS  Google Scholar 

  14. Yan F, Chen Z D. Magnetic coupling constants and spin density maps for heterobinuclear complexes GdCu(Otf)3(bdmap)2(H2O)·THF, [Gd(C4H7ON)4 (H2O)3][Fe(CN)6]·2H2O, and [Gd(C4H7ON)4(H2O)3] [Cr(CN)6]·2H2O: a density functional study. J Phys Chem A, 2000, 104: 6295–6300

    Article  CAS  Google Scholar 

  15. Benelli C, Gatteschi D. Magnetism of lanthanides in molecular materials with transition-metal ions and organic radicals. Chem Rev, 2002, 102: 2369–2388

    Article  CAS  Google Scholar 

  16. Roy L E, Hughbanks T. Magnetic coupling in dinuclear Gd complexes. J Am Chem Soc, 2006, 128(2): 568–575

    Article  CAS  Google Scholar 

  17. Zhao Q H, Ma Y P, Du L, Fang R B. Three novel rare-earth complexes with nitronyl nitroxide radical [RE(hfac)3(NITPhOCH3)2] [RE=GdIII, YIII and ErIII]: syntheses, crystal structures and magnetic properties. Transit Metal Chem, 2006, 31: 593–597

    Article  CAS  Google Scholar 

  18. Amsterdam Density Functional (ADF), version 2002.03. Scientific Computing and Modelling, Theoretical Chemistry, Vrije Universiteit, Amsterdam, 2002

  19. Vosko S H, Wilk L, Nusair M. Accurate spin-dependent electron liquid correlation energies for local spin density calculations: a critical analysis. Can J Phys, 1980, 58: 1200–1211

    Article  CAS  Google Scholar 

  20. Becke A D. Density-functional exchange-energy approximation with correct asymptotic behavior. Phys Rev A, 1988, 38: 3098–3100

    Article  CAS  Google Scholar 

  21. Perdew J P. Density-functional approximation for the correlation energy of the inhomogeneous electron gas. Phys Rev B, 1986, 33: 8822–8824

    Article  Google Scholar 

  22. Caballol R, Castell O, Illas F, Moreira I de P R, Malrieu J P. Remarks on the proper use of the broken symmetry approach to magnetic coupling. J Phys Chem A, 1997, 101: 7860–7866

    Article  CAS  Google Scholar 

  23. Ruiz E, de Graaf C, Alemany P, Alvarez S. Further theoretical evidence for the exceptionally strong ferromagnetic coupling in oxobridged Cu(II) dinuclear complexes. J Phys Chem A, 2002, 106: 4938–4941

    Article  CAS  Google Scholar 

  24. Rodriguez-Fortea A, Alemany P, Alvarez S, Ruiz E. Exchange coupling in halo-bridged dinuclear Cu(II) compounds: A density functional study. Inorg Chem, 2002, 41: 3769–3778

    Article  CAS  Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Beijing National Laboratory for Molecular Sciences, State Key Laboratory of Rare Earth Materials Chemistry and Applications, College of Chemistry and Molecular Engineering, Peking University, Beijing, 100871, China

    Jie Ren, BingWu Wang & ZhiDa Chen

  2. College of Science, Hebei University of Science and Technology, Shijiazhuang, 050018, China

    Jie Ren

Authors
  1. Jie Ren
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. BingWu Wang
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. ZhiDa Chen
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to ZhiDa Chen.

Additional information

Supported by the 973 Project (Grant No. 2006CB601102), and the National Natural Science Foundation of China (Grant No. 20973052)

Rights and permissions

Reprints and permissions

About this article

Cite this article

Ren, J., Wang, B. & Chen, Z. Density functional theory study of the magnetic properties of rare earth complexes: the magnetic coupling mechanism in YIII and GdIII complexes with nitronyl nitroxide. Sci. China Ser. B-Chem. 52, 1961–1968 (2009). https://doi.org/10.1007/s11426-009-0258-x

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s11426-009-0258-x

Keywords

Search

Navigation