Issue 16, 2023

Tuning symmetry and magnetic blocking of an exchange-coupled lanthanide ion in isomeric, tetrametallic complexes: [LnCl6(TiCp2)3]

Abstract

The synthesis and magnetic properties of two pairs of isomeric, exchange-coupled complexes, [LnCl6(TiCp2)3] (Ln = Gd, Tb), are reported. In each isomeric pair, the central lanthanide ion adopts either a pseudo-octahedral (O-Ln) or trigonal prismatic geometry (TP-Ln) yielding complexes with C1 or C3h molecular symmetry, respectively. Ferromagnetic exchange coupling is observed in TP-Ln as indicated by the increases in χmT below 30 K. For TP-Gd, a fit to the susceptibility reveals ferromagnetic coupling between the Gd3+ ion and the Ti3+ ions (J = 2.90(1) cm−1). In contrast to O-Tb, which shows no single-molecule magnetic behavior, the TP-Tb complex presents slow magnetic relaxation with a 100s-blocking temperature of 2.3 K and remanent magnetization at zero field up to 3 K. The calculated electronic structures of both compounds imply that trigonal prismatic geometry of TP-Tb is critical to the observed magnetic behavior.

Graphical abstract: Tuning symmetry and magnetic blocking of an exchange-coupled lanthanide ion in isomeric, tetrametallic complexes: [LnCl6(TiCp2)3]

Supplementary files

Article information

Article type
Edge Article
Submitted
13 Nov 2022
Accepted
23 Mar 2023
First published
23 Mar 2023
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY-NC license

Chem. Sci., 2023,14, 4302-4307

Tuning symmetry and magnetic blocking of an exchange-coupled lanthanide ion in isomeric, tetrametallic complexes: [LnCl6(TiCp2)3]

N. Jiang, D. D. Nakritskaia, J. Xie, A. Ramanathan, S. A. Varganov and H. S. La Pierre, Chem. Sci., 2023, 14, 4302 DOI: 10.1039/D2SC06263A

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