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Synthesis and Magnetic Properties of Bis-Halobenzene Decamethyldysprosocenium Cations.
Corner, Sophie C; Gransbury, Gemma K; Vitorica-Yrezabal, Iñigo J; Whitehead, George F S; Chilton, Nicholas F; Mills, David P.
Afiliación
  • Corner SC; Department of Chemistry, The University of Manchester, Oxford Road, Manchester M13 9PL, U.K.
  • Gransbury GK; Department of Chemistry, The University of Manchester, Oxford Road, Manchester M13 9PL, U.K.
  • Vitorica-Yrezabal IJ; Department of Chemistry, The University of Manchester, Oxford Road, Manchester M13 9PL, U.K.
  • Whitehead GFS; Department of Chemistry, The University of Manchester, Oxford Road, Manchester M13 9PL, U.K.
  • Chilton NF; Department of Chemistry, The University of Manchester, Oxford Road, Manchester M13 9PL, U.K.
  • Mills DP; Department of Chemistry, The University of Manchester, Oxford Road, Manchester M13 9PL, U.K.
Inorg Chem ; 63(21): 9562-9571, 2024 May 27.
Article en En | MEDLINE | ID: mdl-38382535
ABSTRACT
The decamethyldysprosocenium cation, [Dy(Cp*)2]+ (Cp* = {C5Me5}), was a target single-molecule magnet (SMM) prior to the isolation of larger dysprosocenium cations, which have recently shown magnetic memory effects up to 80 K. However, the relatively short Dy···Cp*centroid distances of [Dy(Cp*)2]+, together with the reduced resonance of its vibrational modes with electronic states compared to larger dysprosocenium cations, could lead to more favorable SMM behavior. Here, we report the synthesis and magnetic properties of a series of solvated adducts containing bis-halobenzene decamethyldysprosocenium cations, namely [Dy(Cp*)2(PhX-κ-X)2][Al{OC(CF3)3}4] (X = F or Cl) and [Dy(Cp*)2(C6H4F2-κ2-F,F)(C6H4F2-κ-F)][Al{OC(CF3)3}4]. These complexes were prepared by the sequential reaction of [Dy(Cp*)2(µ-BH4)]∞ with allylmagnesium chloride and [NEt3H][Al{OC(CF3)3}4], followed by recrystallization from parent halobenzenes. The complexes were characterized by powder and single crystal X-ray diffraction, NMR and ATR-IR spectroscopy, elemental analysis, and SQUID magnetometry; experimental data were rationalized by a combination of density functional theory and ab initio calculations. We find that bis-halobenzene adducts of the [Dy(Cp*)2]+ cation exhibit highly bent Cp*···Dy···Cp* angles; these cations are also susceptible to decomposition by C-X (X = F, Cl, Br) activation and displacement of halobenzenes by O-donor ligands. The effective energy barrier to reversal of magnetization measured for [Dy(Cp*)2(PhF-κ-F)2][Al{OC(CF3)3}4] (930(6) cm-1) sets a new record for SMMs containing {Dy(Cp*)2} fragments, though all SMM parameters are lower than would be predicted for an isolated [Dy(Cp*)2]+ cation, as expected due to transverse ligand fields introduced by halobenzenes and the large deviation of the Cp*···Dy···Cp* angle from linearity promoting magnetic relaxation.
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Texto completo: 1 Colección: 01-internacional Base de datos: MEDLINE Idioma: En Revista: Inorg Chem Año: 2024 Tipo del documento: Article País de afiliación: Reino Unido Pais de publicación: Estados Unidos
Texto completo
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Texto completo: 1 Colección: 01-internacional Base de datos: MEDLINE Idioma: En Revista: Inorg Chem Año: 2024 Tipo del documento: Article País de afiliación: Reino Unido Pais de publicación: Estados Unidos