Synthesis, X-Ray Crystal Structures, and Magnetic Properties of a Series of Trinuclear Rare-Earth Hepta-Chloride Clusters

Synthesis, X-Ray Crystal Structures, and Magnetic Properties of a Series of Trinuclear Rare-Earth Hepta-Chloride Clusters

Organometallic rare-earth complexes have attracted considerable attention in recent years due to their unique structures and exceptional magnetic properties. In this study, we report the synthesis and magnetic characteristics of a family of monopentamethylcyclopentadienyl-coordinated trinuclear rare...

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Bibliographic Details
Main Authors: Yingying Pan, You-Song Ding, Lei Li, Zhiping Zheng
Format: Article
Language:English
Published: MDPI AG 2025-05-01
Series:Magnetochemistry
Subjects:
single-molecule magnet
organometallic rare-earth complex
lanthanide chloride cluster
energy barrier
exchange coupling
Online Access:https://www.mdpi.com/2312-7481/11/5/38
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Summary:Organometallic rare-earth complexes have attracted considerable attention in recent years due to their unique structures and exceptional magnetic properties. In this study, we report the synthesis and magnetic characteristics of a family of monopentamethylcyclopentadienyl-coordinated trinuclear rare-earth hepta-chloride clusters [(Li(THF)(Et<sub>2</sub>O))(Cp<sup>*</sup>RE)<sub>3</sub>(<i>μ</i>-Cl)<sub>4</sub>(<i>μ</i><sub>3</sub>-Cl)<sub>2</sub>(<i>μ</i><sub>4</sub>-Cl)] (<b>RE<sub>3</sub></b>: RE =Y, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu; Cp* = pentamethylcyclopentadienide). These clusters were synthesized by reacting LiCp* with RECl<sub>3</sub> in a 1:1 molar ratio within a mixed solvent system (THF: Et<sub>2</sub>O = 1:9), resulting in high solubility in common organic solvents such as DCM, THF, and Et<sub>2</sub>O. Magnetic studies conducted on these paramagnetic clusters reveal the coexistence of ferromagnetic and antiferromagnetic superexchange interactions in <b>Gd<sub>3</sub></b>. Additionally, <b>Dy<sub>3</sub></b> exhibits both ferromagnetic and antiferromagnetic intramolecular dipolar interactions. Notably, slow magnetic relaxation was observed in <b>Dy<sub>3</sub></b> below 23 K under a zero DC applied field with an energy barrier of 125(6) cm<sup>−1</sup>.
ISSN:2312-7481

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