A linear cobalt(II) complex with maximal orbital angular momentum from a non-Aufbau ground state

Orbital angular momentum is a prerequisite for magnetic anisotropy, although in transition metal complexes it is typically quenched by the ligand field. By reducing the basicity of the carbon donor atoms in a pair of alkyl ligands, we synthesized a cobalt(II) dialkyl complex, Co(C(SiMe ONaph) ) (whe...

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Bibliographic Details
Published in:Science (American Association for the Advancement of Science) Vol. 362; no. 6421
Main Authors: Bunting, Philip C, Atanasov, Mihail, Damgaard-Møller, Emil, Perfetti, Mauro, Crassee, Iris, Orlita, Milan, Overgaard, Jacob, van Slageren, Joris, Neese, Frank, Long, Jeffrey R
Format: Journal Article
Language:English
Published: United States 21.12.2018
ISSN:1095-9203, 1095-9203
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Summary:Orbital angular momentum is a prerequisite for magnetic anisotropy, although in transition metal complexes it is typically quenched by the ligand field. By reducing the basicity of the carbon donor atoms in a pair of alkyl ligands, we synthesized a cobalt(II) dialkyl complex, Co(C(SiMe ONaph) ) (where Me is methyl and Naph is a naphthyl group), wherein the ligand field is sufficiently weak that interelectron repulsion and spin-orbit coupling play a dominant role in determining the electronic ground state. Assignment of a non-Aufbau (d , d ) (d , d ) (d ) electron configuration is supported by dc magnetic susceptibility data, experimental charge density maps, and ab initio calculations. Variable-field far-infrared spectroscopy and ac magnetic susceptibility measurements further reveal slow magnetic relaxation via a 450-wave number magnetic excited state.
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ISSN:1095-9203
1095-9203
DOI:10.1126/science.aat7319