TY - JOUR
T1 - Probing Relaxation Dynamics in Five‐Coordinate Dysprosium Single‐Molecule Magnets
AU - Parmar, Vijay S.
AU - Ortu, Fabrizio
AU - Ma, Xiaozhou
AU - Chilton, Nicholas F.
AU - Clérac, Rodolphe
AU - Mills, David P.
AU - Winpenny, Richard E. P.
PY - 2020/6
Y1 - 2020/6
N2 - A new family of five-coordinate lanthanide single-molecule magnets (Ln SMMs) [Dy(Mes*O)2(THF)2X] (Mes*=2,4,6-tri-tert-butylphenyl; X=Cl, 1; Br, 2; I, 3) is reported with energy barriers to magnetic reversal >1200 K. The five-coordinate DyIII ions have distorted square pyramidal geometries, with halide anions on the apex, and two Mes*O ligands mutually trans- to each other, and the two THF molecules forming the second trans- pair. These geometrical features lead to a large magnetic anisotropy in these complexes along the trans-Mes*O direction. QTM and Raman relaxation times are enhanced by varying the apex halide from Cl to Br to I, or by dilution in a diamagnetic yttrium analogue.
AB - A new family of five-coordinate lanthanide single-molecule magnets (Ln SMMs) [Dy(Mes*O)2(THF)2X] (Mes*=2,4,6-tri-tert-butylphenyl; X=Cl, 1; Br, 2; I, 3) is reported with energy barriers to magnetic reversal >1200 K. The five-coordinate DyIII ions have distorted square pyramidal geometries, with halide anions on the apex, and two Mes*O ligands mutually trans- to each other, and the two THF molecules forming the second trans- pair. These geometrical features lead to a large magnetic anisotropy in these complexes along the trans-Mes*O direction. QTM and Raman relaxation times are enhanced by varying the apex halide from Cl to Br to I, or by dilution in a diamagnetic yttrium analogue.
KW - magnetic anisotropy
KW - lanthanides
KW - single-molecule magnets
KW - aryloxides
KW - paramagnetic relaxation
U2 - 10.1002/chem.202001235
DO - 10.1002/chem.202001235
M3 - Article
SN - 0947-6539
VL - 26
SP - 7774
EP - 7778
JO - Chemistry - A European Journal
JF - Chemistry - A European Journal
IS - 35
ER -