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Structural, magnetic and spectral properties of tetrahedral cobalt(ii) silanethiolates: a variety of structures and manifestation of field-induced slow magnetic relaxation

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Abstract

Blue crystals of five heteroleptic cobalt(II) silanethiolates 1–5 have been obtained by the reaction of [Co{SSi(tBuO)3}2(NH3)]2 with aminopyridines and aminomethylpyridines at an appropriate molar ratio and their structural, spectral, thermal and magnetic properties have been established and described. All complexes 1–5 contain Co(II) ions in a tetrahedral CoN2S2 environment formed by (tBuO)3SiS residues and pyridines and present variable structures. Complexes 1–3 are mononuclear [Co{SSi(tBuO)3}2(L1)2] (L1 = 2-aminopyridine 2AP, 3-aminopyridine 3AP, and 4-aminopyridine 4AP). The application of 3AMP and 4AMP (3-aminomethylpyridine and 4-aminomethylpyridine) allows either dinuclear complex 4 [Co{SSi(tBuO)3}2(μ-3AMP)]2 or 1D coordination polymer 5 with the formula of [Co{SSi(tBuO)3}2(μ-4AMP)]n to be obtained. The molecular structures of 1–5 were determined by single-crystal X-ray and powder diffraction, UV-vis and FTIR spectrocopy for solid samples and their thermal properties were characterized by TG-DSC and TG-FTIR methods. The dc and ac magnetic and EPR studies of polycrystalline samples have been performed. For all complexes, the obtained data show a behavior typical of paramagnetic high–spin Co(II) ions in a tetrahedral geometry, with a considerable contribution of the ZFS effect in a low temperature range. All complexes were also probed for SIM behavior. The modeling of the magnetic and EPR data was done for samples 1, 3, 4 and 5 to estimate ZFS parameters. The obtained results imply a negative value of the axial parameter D in complex 4 and positive D values for the rest of the compounds. A comparative magneto-structural analysis of complexes 4 and 5 points to the high sensitivity of the single-ion magnetic anisotropy of tetrahedral Co(II) complexes to subtle changes in the first and second coordination spheres of Co(II) ions.

Graphical abstract: Structural, magnetic and spectral properties of tetrahedral cobalt(ii) silanethiolates: a variety of structures and manifestation of field-induced slow magnetic relaxation

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Article information


Submitted
18 Sep 2019
Accepted
06 Dec 2019
First published
18 Dec 2019

Dalton Trans., 2020, Advance Article
Article type
Paper

Structural, magnetic and spectral properties of tetrahedral cobalt(II) silanethiolates: a variety of structures and manifestation of field-induced slow magnetic relaxation

D. Kowalkowska-Zedler, A. Dołęga, N. Nedelko, R. Łyszczek, P. Aleshkevych, I. Demchenko, J. Łuczak, A. Ślawska-Waniewska and A. Pladzyk, Dalton Trans., 2020, Advance Article , DOI: 10.1039/C9DT03722E

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