Studies of the Temperature Dependence of the Structure and Magnetism of a Hexagonal-Bipyramidal Dysprosium(III) Single-Molecule Magnet

You Song Ding, William J.A. Blackmore, Yuan Qi Zhai, Marcus J. Giansiracusa, Daniel Reta, Inigo Vitorica-Yrezabal, Richard E.P. Winpenny, Nicholas F. Chilton*, Yan Zhen Zheng*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

20 Citations (Scopus)

Abstract

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.
Original languageEnglish
Pages (from-to)227-235
Number of pages9
JournalInorganic Chemistry
Volume61
Issue number1
Early online date23 Dec 2021
DOIs
Publication statusPublished - 10 Jan 2022
Externally publishedYes

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