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Carbon-for-nitrogen substitution (51 at% at most) was achieved in the antiferromagnetic metallic host material Mn(3)ZnN. The various carbon-doped compounds were studied using synchrotron X-ray diffraction, and their electrical resistivities, specific heats, and degrees of magnetization were measured for temperatures of 2-400 K. The sharp antiferromagnetic-to-paramagnetic transition of the host material at 185 K broadened markedly as the carbon content was increased, and a significant ferromagnetic character was found to coexist with the antiferromagnetism when the carbon concentration exceeded 27 at%. This critical magnetic behavior is likely in part due to the increase in the density of states at the Fermi level and the increase in the distance between neighboring Mn atoms. The exact mechanism responsible for the induction of the complicated magnetic state could not be determined. However, the results demonstrate clearly that the chemical tuning of the X site in antiperovskite Mn(3)AX materials is as useful as that of the A and Mn sites and can be used to develop the properties of these materials for practical applications.

The crystal structure of the layered cobalt oxyfluoride Sr(2)CoO(3)F synthesized under high-pressure and high-temperature conditions has been determined from neutron powder diffraction and synchrotron powder diffraction data collected at temperatures ranging from 320 to 3 K. This material adopts the tetragonal space group I4/mmm over the measured temperature range and the crystal structure is analogous to n = 1 Ruddlesden-Popper type layered perovskite. In contrast to related oxyhalide compounds, the present material exhibits the unique coordination environment around the Co metal center: coexistence of square pyramidal coordination around Co and anion disorder between O and F at the apical sites. Magnetic susceptibility and electrical resistivity measurements reveal that Sr(2)CoO(3)F is an antiferromagnetic insulator with the Néel temperature T(N) = 323(2) K. The magnetic structure that has been determined by neutron diffraction adopts a G-type antiferromagnetic order with the propagation vector k = (1/2 1/2 0) with an ordered cobalt moment μ = 3.18(5) μ(B) at 3 K, consistent with the high spin electron configuration for the Co(3+) ions. The antiferromagnetic and electrically insulating states remain robust even against 15%-O substation for F at the apical sites. However, applying pressure exhibits the onset of the metallic state, probably coming from change in the electronic state of square-pyramidal coordinated cobalt.

Perovskite materials provide a large variety of interesting physical properties and applications. Here, we report on unique properties of a fully ordered magnetodielectric double-perovskite, Sc2NiMnO6 (space group P21/n, a = 4.99860 A, b = 5.35281 A, c = 7.34496 A, and β = 90.7915°), exhibiting sequential magnetic transitions at T1 = 35 K and T2 = 17 K. The transition at T1 corresponds to a single-k antiferromagnetic phase with propagation vector k1 = (1/2, 0, 1/2), while the second transition at T2 corresponds to a 2-k magnetic structure with propagation vectors k1 = (1/2, 0, 1/2) and k2 = (0, 1/2, 1/2). Symmetry analysis suggests that the two ordering wave vectors are independent, and calculations imply that k1 is associated with the Mn sublattice and k2 with the Ni sublattice, suggesting that Mn-Ni coupling is very small or absent. A magnetodielectric anomaly at T2 likely arises from an antiferroelectric ordering that results from the exchange-striction between the two magnetic sublattices belonging to k1 and k2. The behavior of Sc2NiMnO6 demonstrates 3d double-perovskites with small A-site cations as a promising avenue in which to search for magnetoelectric materials.

The polycrystalline MO2's (HP-PdF2-type MO2, M = Rh, Os, Pt) with high-pressure PdF2 compounds were successfully synthesized under high-pressure conditions for the first time, to the best of our knowledge. The crystal structures and electromagnetic properties were studied. Previously unreported electronic properties of the polycrystalline HP-PdF2-type RuO2 and IrO2 were also studied. The refined structures clearly indicated that all compounds crystallized into the HP-PdF2-type structure, M(4+)O(2-)2, rather than the pyrite-type structure, M(n+)(O2)(n-) (n4). The MO2 compounds (M = Ru, Rh, Os, Ir) exhibited metallic conduction, while PtO2 was highly insulating, probably because of the fully occupied t2g band. Neither superconductivity nor a magnetic transition was detected down to a temperature of 2 K, unlike the case of 3d transition metal chalcogenide pyrites.

The antiperovskite Mn(3)ZnN is studied by neutron diffraction at temperatures between 50 and 295 K. Mn(3)ZnN crystallizes to form a cubic structure at room temperature (C1 phase). Upon cooling, another cubic structure (C2 phase) appears at around 177 K. Interestingly, the C2 phase disappears below 140 K. The maximum mass concentration of the C2 phase is approximately 85% (at 160 K). The coexistence of C1 and C2 phase in the temperature interval of 140-177 K implies that phase separation occurs. Although the C1 and C2 phases share their composition and lattice symmetry, the C2 phase has a slightly larger lattice parameter (Δa ≈ 0.53%) and a different magnetic structure. The C2 phase is further investigated by neutron diffraction under high-pressure conditions (up to 270 MPa). The results show that the unusual appearance and disappearance of the C2 phase is accompanied by magnetic ordering. Mn(3)ZnN is thus a valuable subject for study of the magneto-lattice effect and phase separation behavior because this is rarely observed in nonoxide materials.

The postspinel mineral MgAl(2)O(4) exists only under the severe pressure conditions in the subducted oceanic lithosphere in the Earth's deep interior. Here we report that its analogous oxide CdRh(2)O(4) exhibits a structural transition to a quenchable postspinel phase under a high pressure of 6 GPa at 1400 °C, which is within the general pressure range of a conventional single-stage multianvil system. In addition, the complex magnetic contributions to the lattice and metal nonstoichiometry that often complicate investigations of other analogues of MgAl(2)O(4) are absent in CdRh(2)O(4). X-ray crystallography revealed that this postspinel phase has an orthorhombic CaFe(2)O(4) structure, thus making it a practical analogue for investigations into the geophysical role of postspinel MgAl(2)O(4). Replacement of Mg(2+) with Cd(2+) appears to be effective in lowering the pressure required for transition, as was suggested for CdGeO(3). In addition, Rh(3+) could also contribute to this reduction, as many analogous Rh oxides of aluminous and silicic minerals have been quenched from lower-pressure conditions.