RESUMO
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.
RESUMO
We present studies of structural, magnetic, and electrical properties of Zn1-x Mn x SnSb2+MnSb nanocomposite ferromagnetic semiconductors with the average Mn-content, [Formula: see text], changing from 0.027 up to 0.138. The magnetic force microscope imaging done at room temperature shows the presence of a strong signal coming from MnSb clusters. Magnetic properties show the paramagnet-ferromagnet transition with the Curie temperature, T C, equal to about 522 K and the cluster-glass behavior with the transition temperature, T CG, equal to about 465 K, both related to MnSb clusters. The magnetotransport studies show that all investigated samples are p-type semiconductors with high hole concentration, p, changing from 10(21) to 10(22) cm(-3). A large increase in the resistivity as a function of the magnetic field is observed at T < 10 K and small magnetic fields, [Formula: see text] mT, for all the studied samples with a maximum amplitude of the magnetoresistance about 460% at T = 1.4 K. The large increase in the resistivity is most probably caused by the appearance of the superconducting state in the samples at T < 4.3 K.
