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Slow magnetic relaxation in hexacoordinated cobalt(ii) field-induced single-ion magnets

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To gain a better insight into the factors affecting the enhancement of the energy barrier in single molecule (single ion) magnets, three hexacoordinate cobalt(II) complexes based on the tridentate ligand 2,6-bis(pyrazol-1-yl)pyridine (pypz) and pseudohalide ions have been synthesized and investigated. It was found that dicyanoamido and azido ligands act as bridges to form a one dimensional network based on a single μ1,5-dca bridge [Co(pypz)(dca)(H2O]·dca (1) and dimer [Co2(pypz)21,1-N3)2(N3)2]·2CH3OH (2), while tcm counterbalanced the charge of [Co(pypz)2]2+ in [Co(pypz)2](tcm)2 (3), where dca = dicyanamide ion; tcm = tricyanomethanide ion, respectively. The DC magnetic data show a sizable magnetic anisotropy, which was confirmed by high-field/high frequency EPR measurements. Two of them are SIMs (1 and 3) and the other one is a SMM (2). All complexes exhibit field induced slow magnetic relaxation with two (1 and 2) or three relaxation channels (3) and an exceptionally long relaxation time for the low-frequency channel upon application of an external field BDC = 0.4, 0.3, and 0.4 T at T = 1.9 K; τ(LF) = 1.9, 2.1 and 0.9 s, respectively. Additionally, the high spin-reversal barriers, U = 103 K for 1 and 95 K for 2, are among the largest for field-induced SIMs for cobalt(II) reported in the literature.

Graphical abstract: Slow magnetic relaxation in hexacoordinated cobalt(ii) field-induced single-ion magnets

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Supplementary files

Article information

27 Feb 2020
21 May 2020
First published
28 May 2020

Inorg. Chem. Front., 2020, Advance Article
Article type
Research Article

Slow magnetic relaxation in hexacoordinated cobalt(II) field-induced single-ion magnets

A. Świtlicka, B. Machura, M. Penkala, A. Bieńko, D. C. Bieńko, J. Titiš, C. Rajnák, R. Boča and A. Ozarowski, Inorg. Chem. Front., 2020, Advance Article , DOI: 10.1039/D0QI00257G

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