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Please use this identifier to cite or link to this item: https://hdl.handle.net/2445/142923
Slow relaxation of magnetization in a bis-mer-tridentate octahedral Co(II) complex
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Reaction of a rigid tridentate ligand o-[(1H-imidazol-2-yl)methylideneamino]phenol (2-H(2)imap) with Co(ClO4) in the presence of NaN3, or Co(NO3)(2) without a base yields [Co-II(2-Himap)(2)] 1 and [Co-III(2-Himap) (2)]NO3 center dot MeOH2, respectively. Both complexes exhibit a mer-octahedral geometry with the cobalt centre being distorted along an octahedral-trigonal prismatic pathway. The packing in 1 and 2 is dominated by H-bonding forming 2D sheets and 1D chains, respectively. Detailed dc and ac magnetic studies indicate that 1 is a field-induced single-ion magnet (SIM) with D = 36.7 cm(-1) and E = 2.0 cm(-1). Extensive ab initio calculations support these conclusions and suggest that relaxation of the magnetization occurs principally through direct quantum tunnelling in the ground state, with the Raman process dominant in an applied field. This contrasts with the recently reported series of mer-[Co(L)(2)] (L = monoanionic NNO donor ligand; Inorg. Chem., 2017, 56, 6056-6066) complexes where D is negative, as these compounds have a more ambiguous geometry, and highlights the importance of supramolecular interactions in subtly altering the coordination sphere thereby impacting the magnetic behaviour.
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SERTPHON, Darunee, et al. Slow relaxation of magnetization in a bis-mer-tridentate octahedral Co(II) complex. Dalton Transactions. 2018. Vol. 47, num. 3, pags. 859-867. ISSN 1477-9226. [consulted: 10 of June of 2026]. Available at: https://hdl.handle.net/2445/142923