Importance of an axial Ln(III)-F bond across the lanthanide series and single-molecule magnet behavior in the Ce and Nd analogues

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Regincós Martí, Emma and Canaj, Angelos B. and Sharma, Tanu and Celmina, Anna and Wilson, Claire and Rajaraman, Gopalan and Murrie, Mark (2022) Importance of an axial Ln(III)-F bond across the lanthanide series and single-molecule magnet behavior in the Ce and Nd analogues. Inorganic Chemistry, 61 (26). pp. 9906-9917. ISSN 1520-510X (https://doi.org/10.1021/acs.inorgchem.2c00556)

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Abstract

The recently reported compound [Dy(III)LF](CF3SO3)2·H2O (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-mol. magnet (SMM) behavior. Following our earlier [Dy(III)LF]2+ work, herein we report the systematic structural and magnetic study of a family of [Ln(III)LF](CF3SO3)2·H2O compounds (Ln(III) = 1-Ce, 2-Pr, 3-Nd, 4-Eu, 5-Tb, 6-Ho, 7-Er, 8-Tm, and 9-Yb). From this series, the Ce(III) and Nd(III) analogs show slow relaxation of the magnetization under an applied d.c. magnetic field, which is modeled using a Raman process. Complete active space SCF theor. calculations are employed to understand the relaxation pathways in 1-Ce and 3-Nd and also reveal a large tunnel splitting for 5-Tb. Addnl. computational studies on model compounds where we remove the axial F- ligand, or replace F- with I-, highlight the importance of the F- ligand in creating a strong axial crystal field for 1-Ce and 3-Nd and for promoting the SMM behavior. Importantly, this systematic study provides insight into the magnetic properties of these lighter lanthanide ions.

ORCID iDs

Regincós Martí, Emma ORCID logoORCID: https://orcid.org/0000-0002-5814-7596, Canaj, Angelos B., Sharma, Tanu, Celmina, Anna, Wilson, Claire, Rajaraman, Gopalan and Murrie, Mark;
CORE (COnnecting REpositories)