Science China Chemistry

, Volume 55, Issue 6, pp 997–1003 | Cite as

One-dimensional lanthanide complexes bridged by nitronyl nitroxide radical ligands with non-chelating nitrogen donors: Structure and magnetic characterization

  • RuiNa Liu
  • Peng Hu
  • LiCun LiEmail author
  • DaiZheng Liao
  • Jean-Pascal Sutter
Articles Special Topic · Molecular Magnetism


A series of new lanthanide-radical complexes [{Ln(hfac)3}2(NITPhIM)2] (Ln = Nd (1), Eu (2), Tb (3), Er (4); hfac = hexafluoroacetylacetonate; NITPhIM = 2-[4-(1-imidazole)phenyl]-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide) have been prepared and characterized. Single crystal X-ray diffraction analyses reveal that these complexes are isostructural with one-dimensional chain structures. These consist in Ln(hfac)3 units bridged by the paramagnetic ligands by the means of coordination of their nitronyl nitroxide groups and imidazole rings. Interestingly, each Ln ion is either bound to two nitronyl nitroxide groups or to two imidazole units, and the different Ln centers alternate along the chain. Magnetic studies show that complex 3 exhibits a single-chain magnet behavior.


nitronyl nitroxide radical lanthanide crystal structure single-chain magnets 


Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.


  1. 1.
    Gatteschi D, Sessoli R. Quantum tunneling of magnetization and related phenomena in molecular materials. Angew Chem Int Ed, 2003, 42: 268–295CrossRefGoogle Scholar
  2. 2.
    Sessoli R, Gatteschi D, Caneschi A, Novak MA. Magnetic bistability in a metal-ion cluster. Nature, 1993, 365: 141–145CrossRefGoogle Scholar
  3. 3.
    Gatteschi D, Sessoli R, Villain J. Molecular Nanomagnets. Oxford: Oxford University Press, 2006CrossRefGoogle Scholar
  4. 4.
    Sessoli R, Tsai HL, Schake AR, Wang S, Vincent JB, Folting K, Gatteschi D, Christou G, Hendrickson DN. High-spin molecules: [Mn12O12(O2CR)16(H2O)4]. J Am Chem Soc, 1993, 115: 1804–1816CrossRefGoogle Scholar
  5. 5.
    Murugesu M, Wernsdorfe W, Abboud KA, Chistou G. New structural motifs in manganese single-molecule magnetism from the use of triethanolamine ligands. Angew Chem Int Ed, 2005, 44: 892–896CrossRefGoogle Scholar
  6. 6.
    Bircher R, Chaboussant G, Dobe C, Güdel HU, Ochsenbein ST, Sieber A, Waldmann O. Single-molecule magnets under pressure. Adv Funct Mater, 2006, 16: 209–220CrossRefGoogle Scholar
  7. 7.
    Aubin SMJ, Dilley SMJ, Pard LI, Krzystek J, Wemple MW, Brunel LC, Maple MB, Christou G, Hendrickson DN. Resonant magnetization tunneling in the trigonal pyramidal MnIVMnIII 3 complex [Mn4O3Cl(O2CCH3)3(dbm)3]. J Am Chem Soc, 1998, 120: 4991–5004CrossRefGoogle Scholar
  8. 8.
    Bogani L, Vindigni A, Sessoli R, Gatteschi D. Single chain magnets: Where to from here? J Mater Chem, 2008, 18: 4750–4761CrossRefGoogle Scholar
  9. 9.
    Miyasaka H, Julve M, Yamashita M, Clérac R. Slow dynamics of the magnetization in one-dimensional coordination polymers: Single-hain magnets. Inorg Chem, 2009, 48: 3420–3437CrossRefGoogle Scholar
  10. 10.
    Miyasaka H, Clérac R. Structures and magnetic properties of bis(hexafluoroacetylacetonato)manganese(II) ligated with N-[3- and 4-(N-tert-butyl-N-oxyaminophenyl)]imidazole. Bull Chem Soc Jpn, 2005, 78: 1725–1728CrossRefGoogle Scholar
  11. 11.
    Leuenberger MN, Loss D. Quantum computing in molecular magnets. Nature, 2001, 410: 789–793CrossRefGoogle Scholar
  12. 12.
    Hill S, Edwards RS, Aliaga AN, Christou G. Quantum coherence in an exchange-coupled dimer of single-molecule magnets. Science, 2003, 302: 1015–1018CrossRefGoogle Scholar
  13. 13.
    Meier F, Levy J, Loss D. Quantum computing with spin cluster qubits. Phys Rev Lett, 2003, 90: 047901CrossRefGoogle Scholar
  14. 14.
    Coulon C, Miyasaka H, Clérac R. Single-Molecule Magnets and Related Phenomena. Winpenny R, ed. Berlin: Springer, 2006, 122: 163–167CrossRefGoogle Scholar
  15. 15.
    Caneschi A, Gatteschi D, Lalioti N, Sangregorio C, Sessoli R, Venturi G, Vindigni A, Rettori A, Pini MG, Novak MA. Cobalt(II)-itronyl nitroxide chains as molecular magnetic nanowires. Angew Chem Int Ed, 2001, 40: 1760–1763CrossRefGoogle Scholar
  16. 16.
    Ishii N, Okamura, Y Chiba S, Nogami T, Ishida T. Giant coercivity in a one-dimensional cobalt-radical coordination magnet. J Am Chem Soc, 2008, 130: 24–27CrossRefGoogle Scholar
  17. 17.
    Benelli C, Gatteschi D. Magnetism of lanthanides in molecular materials with transition-metal ions and organic radicals. Chem Rev, 2002, 102: 2369–2387CrossRefGoogle Scholar
  18. 18.
    Sessoli R, Powell AK. Strategies towards single molecule magnets based on lanthanide ions. Coord Chem Rev, 2009, 253: 2328–2341CrossRefGoogle Scholar
  19. 19.
    Bogani L, Sangregorio C, Sessoli R, Gatteschi D. Molecular engineering for single-chain-magnet behavior in a one-dimensional dysprosium-nitronyl nitroxide compound. Angew Chem Int Ed, 2005, 44: 5817–5821CrossRefGoogle Scholar
  20. 20.
    Bernot K, Bogani L, Caneschi A, Gatteschi D, Sessoli R. A family of rare-earth-based single chain magnets: Playing with anisotropy. J Am Chem Soc, 2006, 128: 7947–7952CrossRefGoogle Scholar
  21. 21.
    Bernot K, Bogani L, Sessoli R, Gatteschi D. [Tm(III)(hfac)3 (NITPhOPh)](infinity): A new member of a lanthanide-based single chain magnets family. Inorg Chim Acta, 2007, 360: 3807–3812CrossRefGoogle Scholar
  22. 22.
    Poneti G, Bernot K, Bogani L, Caneschi A, Sessoli R, Wernsdorferc W, Gatteschi D. A rational approach to the modulation of the dynamics of the magnetisation in a dysprosium-nitronyl-nitroxide radical complex. Chem Commun, 2007, 1807–1809Google Scholar
  23. 23.
    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: 5472–5476CrossRefGoogle Scholar
  24. 24.
    Lescop C, Belorizky E, Luneau D, Rey P. Synthesis, structures, and magneticp roperties of a series of Lanthanum(III) and Gadolinium(III) complexes with chelating benzimidazole-substituted nitronyl nitroxide free radicals. evidence for antiferromagnetic GdIII-radical interactions. Inorg Chem, 2002, 41: 3375–3379CrossRefGoogle Scholar
  25. 25.
    Benelli C, Caneschi A, Gatteschi D, Pardi L, Rey P, Shum DP, Carlin RL. Magnetic properties of lanthanide complexes with nitronyl nitroxides. Inorg Chem, 1989, 28: 272–275CrossRefGoogle Scholar
  26. 26.
    Benelli C, Caneschi A, Gatteschi D. Pardi L. Gadolinium(III) complexes with pyridine-substituted nitronyl nitroxide radicals. Inorg Chem, 1992, 31:741–745CrossRefGoogle Scholar
  27. 27.
    Sutter JP, Kahn ML, 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: 571–576CrossRefGoogle Scholar
  28. 28.
    Kahn ML, Sutter JP, 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: 3413–3421CrossRefGoogle Scholar
  29. 29.
    Tsukuda T, Suzuki T, Kaizaki S. Magnetic interactions in a series of paramagnetic Ln(III) complexes with a chelated imino nitroxide radical. Polyhedron, 2007, 26: 3175–3181CrossRefGoogle Scholar
  30. 30.
    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: 4223–4228CrossRefGoogle Scholar
  31. 31.
    Benelli C, Canesch A. Gatteschi D, Sessoli R, Magnetic interactions and magnetic ordering in rare earth metal nitronyl nitroxide chains. Inorg Chem, 1993, 32: 4797–4801CrossRefGoogle Scholar
  32. 32.
    Liu RN, Li LC, Wang XL, Yang PP, Wang C, Liao DZ, Sutter JP. A linear tetranuclear dysprosium(III) compound showing single-moleculemagnet behaviour. Chem Commun, 2010, 46: 2566–2568CrossRefGoogle Scholar
  33. 33.
    Sheldrick GM. SHELXS 97, Göttingen: University of Göttingen, Germany, 1997Google Scholar
  34. 34.
    Sheldrick GM. SHELXL 97, Göttingen: University of Göttingen, Germany, 1997Google Scholar
  35. 35.
    Llunell M, Casanova D, Cirera J, Bofill J M, Alemany P, Alvarez S, Pinsky M, Avnir D. SHAPE, 1.1b; Barcelona, 2005Google Scholar
  36. 36.
    Wan YH, Zhang LP, Jin LP, Gao S, Lu SZ, High-dimensional architectures from the self-assembly of lanthanideions with benzenedicarboxylates and 1,10-phenanthroline. Inorg Chem, 2003, 42: 4985–4994CrossRefGoogle Scholar
  37. 37.
    Ishimura Y, Inoue K, Koga N, Iwamura H. Structures and magnetic properties of bis(hexafluoroacetylacetonato) manganese(II) ligated with N-[3- and 4-(N-tert-butyl-N-oxyaminophenyl)] imidazole. Chem Lett, 1994, 1693Google Scholar
  38. 38.
    Zhou N, Ma Y, Wang C, Xu GF., Tang JK, Xu XJ, Yan SP, Cheng P, Li LC, Liao DZ. A monometallic tri-spin single-molecule magnet based on rare earth radicals. Dalton Trans, 2009, 8489–8496Google Scholar
  39. 39.
    Bernot K, Luzon J, Bogani L, Etienne M, Sangregorio C, Shanmugam M, Caneschi A, Sessoli R, Gatteschi D. Design, synthesis, and evaluation of an α-helix mimetic library targeting protein-protein interactions. J Am Chem Soc, 2009, 131: 5573–5576CrossRefGoogle Scholar

Copyright information

© Science China Press and Springer-Verlag Berlin Heidelberg 2012

Authors and Affiliations

  • RuiNa Liu
    • 1
  • Peng Hu
    • 1
  • LiCun Li
    • 1
    • 2
    Email author
  • DaiZheng Liao
    • 1
  • Jean-Pascal Sutter
    • 3
  1. 1.Key Laboratory of Advanced Energy Materials Chemistry, Department of ChemistryNankai UniversityTianjinChina
  2. 2.Tianjin Key Laboratory of Metal and Molecule-based Material ChemistryNankai UniversityTianjinChina
  3. 3.UPS, INPT; LCCUniversité de ToulouseToulouseFrance

Personalised recommendations