The temperature and magnetic field dependences of the static magnetization of the polycrystalline rare-earth cobaltites GdCoO₃ and SmCoO₃ have been measured. It is shown that, below room temperature, the magnetization of both compounds derives primarily from the rare-earth ion paramagnetism. The GdCoO₃ and SmCoO₃ compounds have been found to differ substantially in magnetic behavior, which can be traced to differences in their electronic shell structures. The magnetic behavior of GdCoO₃ is close to that of an array of free Gd³⁺ ions, whereas in SmCoO₃ the deviation from the free-ion properties is very large because of the Sm³⁺ ground state being crystal-field split. Van Vleck magnetic susceptibility measurements of SmCoO₃ suggest that the splitting is ∼10 K.

Co₃O₂BO₃ and Co₂FeO₂BO₃ single crystals with a ludwigite structure are fabricated, and their crystal structure and magnetic properties are studied in detail. Substituted ludwigite Co₂FeO₂BO₃ undergoes two-stage magnetic ordering at the temperatures characteristic of Fe₃O₂BO₃ (T _N1 ≈ 110 K, T _N2 ≈ 70 K) rather than Co₃O₂BO₃ (T _N = 42 K). This effect is explained in terms of preferred occupation of nonequivalent crystallographic positions by iron, which was detected by X-ray diffraction. Both materials exhibit a pronounced uniaxial magnetic anisotropy. Crystallographic direction b is an easy magnetization axis. Upon iron substitution, the cobalt ludwigite acquires a very high magnetic hardness.

We have investigated the spin and oxidation states of Co in ${\mathrm{Co}}_3{\mathrm{BO}}_5$ using x-ray magnetic circular dichroism (XMCD) and dc magnetic susceptibility measurements. At low temperatures, XMCD experiments have been performed at the Co $K$-edge in ${\mathrm{Co}}_3{\mathrm{BO}}_5$ and ${\mathrm{Co}}_2{\mathrm{FeBO}}_5$ single crystals in the fully ferrimagnetically ordered phase. The Co ($K$-edge) XMCD signal is found to be related to the ${\mathrm{Co}}^{2+}$ magnetic sublattices in both compounds, providing strong experimental support for the low-spin (LS) ${\mathrm{Co}}^{3+}$ scenario. The paramagnetic susceptibility is highly anisotropic. An estimation of the effective magnetic moment in the temperature range 100–250 K correlates well with two ${\mathrm{Co}}^{2+}$ ions in the high-spin (HS) state and some orbital contribution, while ${\mathrm{Co}}^{3+}$ remains in the LS state. The crystal structure of the ${\mathrm{Co}}_3{\mathrm{BO}}_5$ single crystal has been solved in detail at the $T$ range 296–703 K. The unit cell parameters and volume show anomalies at 500 and 700 K. The octahedral environment of the Co4 site strongly changes with heating. The generalized gradient approximation with Hubbard $U$ correction calculations have revealed that, at low-temperatures, the system is insulating with a band gap of 1.4 eV, and the ${\mathrm{Co}}^{2+}$ ions are in the HS state, while ${\mathrm{Co}}^{3+}$ are in the LS state. At high temperatures ($T$ > 700 K), the charge ordering disappears, and the system becomes metallic with all Co ions in $3d^7$ electronic configuration and HS state.

Single crystals of cobalt oxyborate Co₃BO₅ are synthesized. The results of investigations into the structural, magnetic, and electrical properties are reported. It is found that Co₃BO₅ crystals exhibit two magnetic anomalies at T ₁ = 17 K and T ₂ = 45 K. The temperature dependence of the electrical resistivity is investigated. Deviations both from the activation law of variation in the electrical resistance and from the Mott variable-range hopping conduction are revealed.

Single crystal, needle shaped samples of diamagnetically diluted cobalt ludwigite CoMgGaO2BO3 have been grown by the flux method. X-ray diffraction and both dc and ac magnetic measurements are described. The unit cell volume changes significantly with dilution, from 328.31 Å3 for the parent compound Co3O2BO3 to 345.46 Å3 for CoMgGaO2BO3. The magnetic transition temperature is considerably lower for the latter compound (25 K against 43 K for Co2O2BO3). The dc magnetization temperature dependences are split between the field cooled and zero-field cooled regimes and the ac magnetic susceptibility temperature curves are frequency dependent, which indicates possible spin-glass freezing in the magnetic system.

Single crystals of cobalt ludwigite Co₃O₂BO₃ with diamagnetic substitution of Ga³⁺ ions for a part of the cobalt ions have been grown by the flux method. A detailed investigation of the crystal structure and magnetic properties of the compound has been carried out. A preferred character of the occupation of nonequivalent crystallographic positions by gallium has been revealed. It has been found that the effective magnetic moment and the magnetic ordering temperature are decreased compared to those in the original crystal of the Co₃O₂BO₃ ludwigite. It has been noted that the pronounced magnetic anisotropy observed in the crystallographic ab plane of the original material of the Co₃O₂BO₃ composition disappears in the presence of gallium.