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Luminescence and single-molecule magnet behavior in lanthanide complexes involving a tetrathiafulvalene-fused dipyridophenazine ligand.
Pointillart, Fabrice; Jung, Julie; Berraud-Pache, Romain; Le Guennic, Boris; Dorcet, Vincent; Golhen, Stéphane; Cador, Olivier; Maury, Olivier; Guyot, Yannick; Decurtins, Silvio; Liu, Shi-Xia; Ouahab, Lahcène.
Afiliação
  • Pointillart F; †Institut des Sciences Chimiques de Rennes UMR 6226 CNRS-Université de Rennes 1, 35042 Rennes Cedex, France.
  • Jung J; †Institut des Sciences Chimiques de Rennes UMR 6226 CNRS-Université de Rennes 1, 35042 Rennes Cedex, France.
  • Berraud-Pache R; †Institut des Sciences Chimiques de Rennes UMR 6226 CNRS-Université de Rennes 1, 35042 Rennes Cedex, France.
  • Le Guennic B; †Institut des Sciences Chimiques de Rennes UMR 6226 CNRS-Université de Rennes 1, 35042 Rennes Cedex, France.
  • Dorcet V; †Institut des Sciences Chimiques de Rennes UMR 6226 CNRS-Université de Rennes 1, 35042 Rennes Cedex, France.
  • Golhen S; †Institut des Sciences Chimiques de Rennes UMR 6226 CNRS-Université de Rennes 1, 35042 Rennes Cedex, France.
  • Cador O; †Institut des Sciences Chimiques de Rennes UMR 6226 CNRS-Université de Rennes 1, 35042 Rennes Cedex, France.
  • Maury O; §Laboratoire de Chimie, l'ENS-LYON-UMR 5182, 46 Allée d'Italie, 69364 Lyon Cedex 07, France.
  • Guyot Y; ∥Institut Lumière Matière, UMR 5306 CNRS-Université de Lyon 1, 10 rue Ada Byron, 69622 Villeurbanne Cedex, France.
  • Decurtins S; ‡Departement für Chemie und Biochemie, Universität Bern, Freiestrasse 3, CH-3012 Bern, Switzerland.
  • Liu SX; ‡Departement für Chemie und Biochemie, Universität Bern, Freiestrasse 3, CH-3012 Bern, Switzerland.
  • Ouahab L; †Institut des Sciences Chimiques de Rennes UMR 6226 CNRS-Université de Rennes 1, 35042 Rennes Cedex, France.
Inorg Chem ; 54(11): 5384-97, 2015 Jun 01.
Artigo em Inglês | MEDLINE | ID: mdl-25965094
ABSTRACT
The reaction between the TTF-fused dipyrido[3,2-a2',3'-c]phenazine (dppz) ligand (L) and 1 equiv of Ln(hfac)3·2H2O (hfac(-) = 1,1,1,5,5,5-hexafluoroacetyacetonate) or 1 equiv of Ln(tta)3·2H2O (tta(-) = 2-thenoyltrifluoroacetonate) (Ln(III) = Dy(III) or Yb(III)) metallic precursors leads to four mononuclear complexes of formula [Ln(hfac)3(L)]·C6H14 (Ln(III) = Dy(III) (1), Yb(III) (2)) and [Ln(tta)3(L)]·C6H14 (Ln(III) = Dy(III) (3), Yb(III) (4)), respectively. Their X-ray structures reveal that the Ln(III) ion is coordinated to the bischelating nitrogenated coordination site and adopts a D4d coordination environment. The dynamic magnetic measurements show a slow relaxation of the Dy(III) magnetization for 1 and 3 with parameters highlighting a slower relaxation for 3 than for 1 (τ0 = 4.14(±1.36) × 10(-6) and 1.32(±0.07) × 10(-6) s with Δ = 39(±3) and 63.7(±0.7) K). This behavior as well as the orientation of the associated magnetic anisotropy axes have been rationalized on the basis of both crystal field splitting parameters and ab initio SA-CASSCF/RASSI-SO calculations. Irradiation of the lowest-energy HOMO → LUMO ILCT absorption band induces a (2)F5/2 → (2)F7/2 Yb-centered emission for 2 and 4. For these Yb(III) compounds, Stevens operators method has been used to fit the thermal variation of the magnetic susceptibilities, and the resulting MJ splittings have been correlated with the emission lines.

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Texto completo: Disponível Coleções: Bases de dados internacionais Base de dados: MEDLINE Idioma: Inglês Revista: Inorg Chem Ano de publicação: 2015 Tipo de documento: Artigo País de afiliação: França