New Antiferromagnetic Perovskite CaCo₃V₄O₁₂ Prepared at High-Pressure and High-Temperature Conditions

A new perovskite, CaCo²⁺₃V⁴⁺₄O₁₂, has been synthesized at high-pressure and high-temperature (HP-HT) conditions. The properties of this perovskite were examined by a range of techniques. CaCo₃V₄O₁₂ was found to adopt a double-perovskite cubic lattice [<i>a</i> = 7.3428(6) Å] with <i>Im</i>3̅ symmetry. We have established that this new perovskite is stable at ambient conditions, and its oxidation and/or decomposition at ambient pressure begins above 500 °C. It undergoes an abrupt antiferromagnetic transition around 98 K. Electrical resistivity data suggest semimetallic conductivity in the temperature range of 1.6–370 K. We have established that the Co²⁺ ions in CaCo₃V₄O₁₂ are in the high-spin state with a sizable orbital moment, even though their square-planar oxygen coordination could be more suitable for the low-spin state, which is prone to Jahn–Teller distortion. Electrical resistivity curves also exhibit a distinct steplike feature around 100 K. CaCo₃V₄O₁₂ is a first example of perovskite in which the sites A′ are fully occupied by Co²⁺ ions, and hence its synthesis opens the door to a new class of double perovskites, ACo₃B₄O₁₂, that may be derived by chemical substitution of the A sublattice by lanthanides, sodium, strontium, and bismuth and by other elements and/or of the B sublattice by some other transition metals