Issue 14, 2023

Strong magnetic exchange coupling in Ln2 metallocenes attained by the trans-coordination of a tetrazinyl radical ligand

Abstract

A combination of high-performing lanthanide metallocenes and tetrazine-based radical ligands leads to a new series of radical-bridged dinuclear lanthanide metallocenes; [(Cp*2LnIII)2(bpytz˙)][BPh4] (where Ln = Gd (1), Tb (2), Dy (3) and Y (4); Cp* = pentamethylcyclopentadienyl; bpytz = 3,6-bis(3,5-dimethyl-pyrazolyl)-1,2,4,5-tetrazine). The formation of the radical species is achieved via a controlled, stepwise synthesis and verified in all complexes by X-ray crystallography and SQUID magnetometry, as well as EPR spectroscopy of 4. Through the judicious choice of the Cp* ancillary ligands and by taking advantage of the steric effects imposed by their bulkiness, we were able to promote the trans coordination mode of the bpytz˙ radical anion that enables stronger magnetic exchange coupling compared to the cis fashion. This yields a JGd–rad = −14.0 cm−1 in 1, which is the strongest exchange coupling observed in organic monoanionic radical-bridged lanthanide metallocene systems. The strong Ln-rad exchange coupling was further confirmed by high-frequency EPR (HF-EPR) spectroscopy and broken-symmetry (BS) density functional theory (DFT) calculations. This combined with the highly anisotropic nature of TbIII and DyIII ions in 2 and 3, respectively, leads to strong SMM behavior and slow relaxation of the magnetization at zero fields.

Graphical abstract: Strong magnetic exchange coupling in Ln2 metallocenes attained by the trans-coordination of a tetrazinyl radical ligand

Supplementary files

Article information

Article type
Research Article
Submitted
16 Feb 2023
Accepted
16 Jun 2023
First published
16 Jun 2023

Inorg. Chem. Front., 2023,10, 4197-4208

Author version available

Strong magnetic exchange coupling in Ln2 metallocenes attained by the trans-coordination of a tetrazinyl radical ligand

N. Mavragani, A. A. Kitos, J. Hrubý, S. Hill, A. Mansikkamäki, J. O. Moilanen and M. Murugesu, Inorg. Chem. Front., 2023, 10, 4197 DOI: 10.1039/D3QI00290J

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