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

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Atanasov,  Mihail
Research Group Atanasov, Max-Planck-Institut für Kohlenforschung, Max Planck Society;
Institute of General and Inorganic Chemistry, Bulgarian Academy of Sciences, Academy Georgi Bontchev;

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Neese,  Frank
Research Department Neese, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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Citation

Bunting, P. C., Atanasov, M., Damgaard-Møller, E., Perfetti, M., Crassee, I., Orlita, M., et al. (2018). A linear cobalt(II) complex with maximal orbital angular momentum from a non-Aufbau ground state. Science, 362(6421): eaat7319. doi:10.1126/science.aat7319.


Cite as: https://hdl.handle.net/21.11116/0000-0002-BF41-E
Abstract
Orbital angular momentum is a prerequisite for magnetic anisotropy, although in transition metal complexes it is typically quenched by the ligand field. Here, by reducing the basicity of the carbon donor atoms in a pair of alkyl ligands, we synthesize a cobalt(II) dialkyl complex, Co(C(SiMe2ONaphthyl)3)2 (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 (dx2–y2, dxy)3(dxz, dyz)3(dz2)1 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.