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Issue 12, 2015
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Observation of the single-ion magnet behavior of d8 ions on two-coordinate Co(I)–NHC complexes

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Abstract

The slow magnetic relaxation typical for single-ion magnets has been known for certain low-coordinate 3d metal complexes with d6, d7, and d9 electronic configurations, but never for d8 complexes. Herein, we report a study on two-coordinate d8 cobalt(I)–N-heterocyclic carbene complexes, for which slow magnetic relaxation behavior was observed for [Co(IMes)2][BPh4] (IMes: 1,3-dimesitylimidazol-2-ylidene) under an applied dc field. The system represents the first d8 single-ion magnet, and features a fitted energy barrier of Ueff = 21.3 cm−1 and pre-exponential factor of τ0 = 6.6 × 10−6 s. The analog two-coordinate cobalt(I) complexes with different NHC ligands, [Co(sIMes)2][BPh4] (sIMes: 1,3-dimesitylimidazolin-2-ylidene) and [Co(IAd)2][BArF4] (IAd: 1,3-dimesitylimidazol-2-ylidene; BArF4: tetra(3,5-ditrifluoromethylphenyl)borate), do not show such single-ion magnet behaviour. Ab initio calculations imply that the dihedral angle between the two NHC planes and the degree of unsaturation of the NHC ligands can dramatically alter the D value of the two-coordinate cobalt(I)–NHC ions, possibly via changing of the Co–NHC π-interactions, and hence affect the spin–orbit coupling splitting.

Graphical abstract: Observation of the single-ion magnet behavior of d8 ions on two-coordinate Co(i)–NHC complexes

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Publication details

The article was received on 19 Jul 2015, accepted on 10 Sep 2015 and first published on 10 Sep 2015


Article type: Edge Article
DOI: 10.1039/C5SC02611C
Citation: Chem. Sci., 2015,6, 7156-7162
  • Open access: Creative Commons BY license
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    Observation of the single-ion magnet behavior of d8 ions on two-coordinate Co(I)–NHC complexes

    Y. Meng, Z. Mo, B. Wang, Y. Zhang, L. Deng and S. Gao, Chem. Sci., 2015, 6, 7156
    DOI: 10.1039/C5SC02611C

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