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(SiMe2ONaph)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.
A linear cobalt(II) complex with maximal orbital angular momentum from a non-Aufbau ground state / Bunting P.C.; Atanasov M.; Damgaard-Moller E.; Perfetti M.; Crassee I.; Orlita M.; Overgaard J.; Van Slageren J.; Neese F.; Long J.R.. - In: SCIENCE. - ISSN 0036-8075. - ELETTRONICO. - 362:(2018), pp. 1378-+. [10.1126/science.aat7319]
A linear cobalt(II) complex with maximal orbital angular momentum from a non-Aufbau ground state
Perfetti M.Membro del Collaboration Group
;
2018
Abstract
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(SiMe2ONaph)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.
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