Marti, Emma Regincos, Canaj, Angelos B ORCID: 0000-0002-4944-7909, Sharma, Tanu, Celmina, Anna, Wilson, Claire, Rajaraman, Gopalan and Murrie, Mark
(2022)
Importance of an Axial Ln<SUP>III</SUP>-F Bond across the Lanthanide Series and Single-Molecule Magnet Behavior in the Ce and Nd Analogues.
INORGANIC CHEMISTRY, 61 (26).
pp. 9906-9917.
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Importance of an Axial LnsupIIIsup-F Bond across the Lanthanide Series and Single-Molecule Magnet Behavior in the Ce and Nd .pdf - Published version Download (2MB) | Preview |
Abstract
The recently reported compound [Dy<sup>III</sup>LF](CF<sub>3</sub>SO<sub>3</sub>)<sub>2</sub>·H<sub>2</sub>O (L = 1,4,7,10-tetrakis(2-pyridylmethyl)-1,4,7,10-tetraaza-cyclododecane) displays a strong axial magnetic anisotropy, due to the short axial Dy-F bond, and single-molecule magnet (SMM) behavior. Following our earlier [Dy<sup>III</sup>LF]<sup>2+</sup> work, herein we report the systematic structural and magnetic study of a family of [Ln<sup>III</sup>LF](CF<sub>3</sub>SO<sub>3</sub>)<sub>2</sub>·H<sub>2</sub>O compounds (Ln(III) = <b>1</b>-Ce, <b>2</b>-Pr, <b>3</b>-Nd, <b>4</b>-Eu, <b>5</b>-Tb, <b>6</b>-Ho, <b>7</b>-Er, <b>8</b>-Tm, and <b>9</b>-Yb). From this series, the Ce(III) and Nd(III) analogues show slow relaxation of the magnetization under an applied direct current magnetic field, which is modeled using a Raman process. Complete active space self-consistent field theoretical calculations are employed to understand the relaxation pathways in <b>1</b>-Ce and <b>3</b>-Nd and also reveal a large tunnel splitting for <b>5</b>-Tb. Additional computational studies on model compounds where we remove the axial F<sup>-</sup> ligand, or replace F<sup>-</sup> with I<sup>-</sup>, highlight the importance of the F<sup>-</sup> ligand in creating a strong axial crystal field for <b>1</b>-Ce and <b>3</b>-Nd and for promoting the SMM behavior. Importantly, this systematic study provides insight into the magnetic properties of these lighter lanthanide ions.
Item Type: | Article |
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Uncontrolled Keywords: | Rare Diseases |
Divisions: | Faculty of Science and Engineering > School of Physical Sciences |
Depositing User: | Symplectic Admin |
Date Deposited: | 22 Jul 2022 14:42 |
Last Modified: | 17 Mar 2024 14:32 |
DOI: | 10.1021/acs.inorgchem.2c00556 |
Open Access URL: | https://pubs.acs.org/doi/10.1021/acs.inorgchem.2c0... |
Related URLs: | |
URI: | https://livrepository.liverpool.ac.uk/id/eprint/3159189 |