TY - JOUR
T1 - Studies of the Temperature Dependence of the Structure and Magnetism of a Hexagonal-Bipyramidal Dysprosium(III) Single-Molecule Magnet
AU - Ding, You Song
AU - Blackmore, William J.A.
AU - Zhai, Yuan Qi
AU - Giansiracusa, Marcus J.
AU - Reta, Daniel
AU - Vitorica-Yrezabal, Inigo
AU - Winpenny, Richard E.P.
AU - Chilton, Nicholas F.
AU - Zheng, Yan Zhen
N1 - Publisher Copyright:
© 2021 American Chemical Society.
PY - 2022/1/10
Y1 - 2022/1/10
N2 - The hexagonal-bipyramidal lanthanide(III) complex [Dy(OtBu)Cl(18-C-6)][BPh4] (1; 18-C-6 = 1,4,7,10,13,16-hexaoxacyclooctadecane ether) displays an energy barrier for magnetization reversal (Ueff) of ca. 1000 K in a zero direct-current field. Temperature-dependent X-ray diffraction studies of 1 down to 30 K reveal bending of the Cl-Ln-OtBu angle at low temperature. Using ab initio calculations, we show that significant bending of the O-Dy-Cl angle upon cooling from 273 to 100 K leads to a ca. 10% decrease in the energy of the excited electronic states. A thorough exploration of the temperature and field dependencies of the magnetic relaxation rate reveals that magnetic relaxation is dictated by five mechanisms in different regimes: Orbach, Raman-I, quantum tunnelling of magnetization, and Raman-II, in addition to the observation of a phonon bottleneck effect.
AB - The hexagonal-bipyramidal lanthanide(III) complex [Dy(OtBu)Cl(18-C-6)][BPh4] (1; 18-C-6 = 1,4,7,10,13,16-hexaoxacyclooctadecane ether) displays an energy barrier for magnetization reversal (Ueff) of ca. 1000 K in a zero direct-current field. Temperature-dependent X-ray diffraction studies of 1 down to 30 K reveal bending of the Cl-Ln-OtBu angle at low temperature. Using ab initio calculations, we show that significant bending of the O-Dy-Cl angle upon cooling from 273 to 100 K leads to a ca. 10% decrease in the energy of the excited electronic states. A thorough exploration of the temperature and field dependencies of the magnetic relaxation rate reveals that magnetic relaxation is dictated by five mechanisms in different regimes: Orbach, Raman-I, quantum tunnelling of magnetization, and Raman-II, in addition to the observation of a phonon bottleneck effect.
UR - https://www.scopus.com/pages/publications/85122493288
U2 - 10.1021/acs.inorgchem.1c02779
DO - 10.1021/acs.inorgchem.1c02779
M3 - 文章
C2 - 34939782
AN - SCOPUS:85122493288
SN - 0020-1669
VL - 61
SP - 227
EP - 235
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 1
ER -