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Switching of easy-axis to easy-plane anisotropy in cobalt(ii) complexes

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Switching of easy-axis to easy-plane anisotropy in cobalt(ii) complexes

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dc.contributor.author	Wu, Yuewei
dc.contributor.author	Xi, Jing
dc.contributor.author	Xiao, Tongtong
dc.contributor.author	Ferrando Soria, Jesús
dc.contributor.author	Ouyang, Zhongwen
dc.contributor.author	Wang, Zhenxing
dc.contributor.author	Luo, Shuchang
dc.contributor.author	Liu, Xiangyu
dc.contributor.author	Pardo Marín, Emilio
dc.date.accessioned	2022-11-09T16:13:53Z
dc.date.available	2022-11-09T16:13:53Z
dc.date.issued	2021
dc.identifier.citation	Wu, Yuewei Xi, Jing Xiao, Tongtong Ferrando Soria, Jesús Ouyang, Zhongwen Wang, Zhenxing Luo, Shuchang Liu, Xiangyu Pardo Marín, Emilio 2021 Switching of easy-axis to easy-plane anisotropy in cobalt(ii) complexes Inorganic Chemistry Frontiers 8 5158 5168
dc.identifier.uri	https://hdl.handle.net/10550/84436
dc.description.abstract	A tetranuclear cubane-type complex [Co4(ntfa)4(CH3O)4(CH3OH)4] (1) with a {Co4O4} core, and a mononuclear complex [Co(ntfa)2(CH3OH)2] (2) have been rationally obtained by adjusting the ratio of the β-diketonate and Co(II) ions, with the synthetic processes being monitored by in situ microcalorimetry. Then, following synthetic conditions to obtain 2, but using three distinct N-donor coligands - 2,2'-bipyridyl (bpy), 6,6'-dimethyl-2,2'-bipyridyl (6,6-(CH3)2-bpy) and 5,5'-dimethyl-2,2'-bipyridyl (5,5-(CH3)2-bpy) - three novel mononuclear complexes have been obtained, [Co(ntfa)2(bpy)2] (3), [Co(ntfa)2(6,6-(CH3)2- bpy)2] (4) and [Co(ntfa)2(5,5-(CH3)2-bpy)2] (5). The introduction of different capping coligands - as singlecrystal X-ray crystallography ascertains - fine-tunes the structures, with changes in both the distortion degree of the coordination geometry and the intermolecular interactions, which have a direct impact on the magnetic properties of these complexes. Magnetic investigations reveal field-induced single-ion magnet behavior in all complexes with distinct energy barriers (Ueff) −39.06 (1), 36.65 (2), 36.32 (3), 28.26 (4) and 15.85 K (5). Magnetic experiments together with HF-EPR measurements and theoretical calculations demonstrate that 2 features easy-axis magnetic anisotropy (D = −60.48 cm−1), whereas 3-5 show easy-plane magnetic anisotropies − D = +70.77 cm−1 for 3, +35.71 cm−1 for 4, and +51.28 cm−1 for 5. To our knowledge, such reversal of anisotropic nature driven by coligands is unprecedented.
dc.language.iso	eng
dc.relation.ispartof	Inorganic Chemistry Frontiers, 2021, vol. 8, p. 5158-5168
dc.subject	Química
dc.subject	Cobalt
dc.title	Switching of easy-axis to easy-plane anisotropy in cobalt(ii) complexes
dc.type	journal article	es_ES
dc.date.updated	2022-11-09T16:13:53Z
dc.identifier.doi	10.1039/D1QI01208H
dc.identifier.idgrec	150576
dc.rights.accessRights	open access	es_ES