Correlating Electronic Structure and Magnetic Anisotropy in Actinide Complexes [An(COT)2], AnIII/IV = U, Np, and Pu

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The electronic structures and magnetic anisotropies for compounds [An(COT)2] (An = UIII/UIV, NpIII/NpIV and PuIII/PuIV, COT = cyclooctatetraene) are characterized using scalar relativistic density functional theory calculations and second-order perturbation theory based on a complete active space self-consistent field reference including spin-orbit coupling. The degree of participation of 5f orbitals in actinide-ligand bonding and the associated metal-ligand covalency is found to trend as U > Np ≥ Pu for both the tetra-positive and tripositive An complexes. A spin-Hamiltonian analysis indicates only weak single-molecule magnet (SMM) characteristics for [U(COT)2]- and [Np(COT)2] complexes and no significant SMM behavior for the other complexes. The weak SMM behavior in [U(COT)2]- and [Np(COT)2] is attributed to a subtle interplay between local symmetry and ligand-field splitting. Such a result suggests that magnetic anisotropy in 5f3 ions can be modulated in general by electrostatic ligand field design. In particular, σ-donor ligands oriented 180 degrees relative to one another will have a maximal influence on the 5f-orbital ligand field splitting, while πdonors like cyclopentadiene and COT generate ligand field influences that have more acute angles associated with corresponding atoms on the individual ligands. These observations rationalize the differences in SMM characteristics for [U(BcMe)3] (BcMe- = dihydrobis(methylimidazolyl)borate) and [U(BpMe)3] (BpMe- = dihydrobis(methylpyrazolyl)borate) and indicate strategies to design new actinide-based SMMs with high magnetic relaxation barriers.

Original languageEnglish (US)
Pages (from-to)6815-6825
Number of pages11
JournalInorganic chemistry
Issue number10
StatePublished - May 18 2020

Bibliographical note

Funding Information:
This work was funded by the Division of Chemical Sciences, Geosciences, and Biosciences, Office of Basic Energy Sciences of the U.S. Department of Energy through Grant No. USDOE/DE-SC002183. We thank the Minnesota Supercomputing Facility (MSI) for the computing resources.

Publisher Copyright:
Copyright © 2020 American Chemical Society.

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  • Journal Article

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