Issue 32, 2024

4f-Orbital mixing increases the magnetic susceptibility of Cp′3Eu

Abstract

Traditional models of lanthanide electronic structure suggest that bonding is predominantly ionic, and that covalent orbital mixing is not an important factor in determining magnetic properties. Here, 4f orbital mixing and its impact on the magnetic susceptibility of Cp′3Eu (Cp′ = C5H4SiMe3) was analyzed experimentally using magnetometry and X-ray absorption spectroscopy (XAS) methods at the C K-, Eu M5,4-, and L3-edges. Pre-edge features in the experimental and TDDFT-calculated C K-edge XAS spectra provided unequivocal evidence of C 2p and Eu 4f orbital mixing in the π-antibonding orbital of a′ symmetry. The charge-transfer configurations resulting from 4f orbital mixing were identified spectroscopically by using Eu M5,4-edge and L3-edge XAS. Modeling of variable-temperature magnetic susceptibility data showed excellent agreement with the XAS results and indicated that increased magnetic susceptibility of Cp′3Eu is due to removal of the degeneracy of the 7F1 excited state due to mixing between the ligand and Eu 4f orbitals.

Graphical abstract: 4f-Orbital mixing increases the magnetic susceptibility of Cp′3Eu

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Article information

Article type
Edge Article
Submitted
25 Feb 2024
Accepted
05 Jun 2024
First published
11 Jun 2024
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., 2024,15, 12667-12675

4f-Orbital mixing increases the magnetic susceptibility of Cp′3Eu

S. O. Gunther, Y. Qiao, P. W. Smith, S. R. Ciccone, A. S. Ditter, D. N. Huh, L. M. Moreau, D. K. Shuh, T. Sun, P. L. Arnold, C. H. Booth, W. A. de Jong, W. J. Evans, W. W. Lukens and S. G. Minasian, Chem. Sci., 2024, 15, 12667 DOI: 10.1039/D4SC01300J

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