TY - JOUR
T1 - Probing relaxation dynamics in five-coordinate dysprosium single-molecule magnets
AU - Parmar, Vijay
AU - Ortu, Fabrizio
AU - Ma, Xiaozhou
AU - Chilton, Nicholas
AU - Clerac, Rodolphe
AU - Mills, David Paul
AU - Winpenny, Richard
PY - 2020
Y1 - 2020
N2 - We report a new family of five‐coordinate Lanthanide Single‐Molecule Magnets (Ln SMMs) [Dy(Mes*O) 2 (THF) 2 X] (Mes*= 2,4,6‐tri‐tert‐butylphenyl; X = Cl, 1 ; Br, 2 ; I, 3 ) with energy barriers to magnetic reversal amongst the highest reported for any SMM to date. The five‐coordinate Dy(III) 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 giving Orbach energy barriers above 1200 K. QTM and Raman relaxation times are significantly enhanced by varying the apex halide from Cl to Br to I, or by simple dilution in a diamagnetic yttrium analogue.
AB - We report a new family of five‐coordinate Lanthanide Single‐Molecule Magnets (Ln SMMs) [Dy(Mes*O) 2 (THF) 2 X] (Mes*= 2,4,6‐tri‐tert‐butylphenyl; X = Cl, 1 ; Br, 2 ; I, 3 ) with energy barriers to magnetic reversal amongst the highest reported for any SMM to date. The five‐coordinate Dy(III) 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 giving Orbach energy barriers above 1200 K. QTM and Raman relaxation times are significantly enhanced by varying the apex halide from Cl to Br to I, or by simple dilution in a diamagnetic yttrium analogue.
U2 - 10.1002/chem.202001235
DO - 10.1002/chem.202001235
M3 - Article
SN - 0947-6539
JO - Chemistry - A European Journal
JF - Chemistry - A European Journal
ER -