University of Oulu

Errulat, D., Harriman, K., Gálico, D., Ovens, J., Mansikkamäki, A., Murugesu, M. (2021) Aufbau vs. non-Aufbau ground states in two-coordinate d7 single-molecule magnets. Inorg. Chem. Front.,8, 5076-5085.

Aufbau vs. non-Aufbau ground states in two-coordinate d⁷ single-molecule magnets

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Author: Errulat, Dylan1; Harriman, Katie L. M.1; Gálico, Diogo A.1;
Organizations: 1Department of Chemistry and Biomolecular Sciences, University of Ottawa, Ottawa, ON K1N 6N5, Canada
2NMR Research Unit, University of Oulu, P.O. Box 3000, 90014 Oulu, Finland
Format: article
Version: accepted version
Access: open
Online Access: PDF Full Text (PDF, 1 MB)
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Language: English
Published: Royal Society of Chemistry, 2021
Publish Date: 2022-10-12


Single-molecule magnets (SMMs) with d⁷ electronic configurations often require designer ligands to satisfy the metals electronic conditions to achieve large angular momentum. Herein, the slow relaxation of the magnetization in two d⁷ metal complexes in near identical ligand fields is achieved from divergent origins. The two compounds, [CoII{N(SiMePh₂)₂}₂] and [K(2,2,2-crypt)][FeI{N(SiMePh₂)₂}₂] (2,2,2-crypt = 2,2,2-cryptand), display unusual electronic configurations giving rise to SMM behavior originating either from 3d–4s orbital mixing or a non-Aufbau ground state. The chracteristics contributing to the rare non-Aufbau ground state configurations are illuminated by the use of a highly donating amido-ligand, which would be expected to significantly split the respective orbitals. Magnetic circular dichroism provides experimental support for ab initio determined electronic structures. Moreover, computational models reveal that the relative electronic configurations are largely retained independently of coordination geometry, provided that some degree of pseudo-linearity is retained. Thus, providing generalized design principles in the pursuit of linear d⁷ SMMs.

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Series: Inorganic chemistry frontiers
ISSN: 2052-1545
ISSN-E: 2052-1553
ISSN-L: 2052-1545
Volume: 8
Pages: 5076 - 5085
DOI: 10.1039/D1QI00912E
Type of Publication: A1 Journal article – refereed
Field of Science: 114 Physical sciences
116 Chemical sciences
Funding: We are grateful to the University of Ottawa, Natural Sciences and Engineering Research Council of Canada, the Canadian Foundation for Innovation, the Magnus Ehrnrooth Foundation, as well as the University of Oulu (Kvantum Institute) for the funding of this work.
Copyright information: © 2021 The Royal Society of Chemistry. The final authenticated version is available online at