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

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.