Structural and magnetic phase transitions in the A(n)B(n)O(3n-2) anion-deficient perovskites Pb2Ba2BiFe5O13 and Pb(1.5)Ba(2.5)Bi2Fe6O16.

Novel anion-deficient perovskite-based ferrites Pb2Ba2BiFe5O13 and Pb(1.5)Ba(2.5)Bi2Fe6O16 were synthesized by solid-state reaction in air. Pb2Ba2BiFe5O13 and Pb(1.5)Ba(2.5)Bi2Fe6O16 belong to the perovskite-based A(n)B(n)O(3n-2) homologous series with n = 5 and 6, respectively, with a unit cell related to the perovskite subcell a(p) as a(p)√2 × a(p) × na(p)√2. Their structures are derived from the perovskite one by slicing it with 1/2[110]p(101)p crystallographic shear (CS) planes. The CS operation results in (101)p-shaped perovskite blocks with a thickness of (n - 2) FeO6 octahedra connected to each other through double chains of edge-sharing FeO5 distorted tetragonal pyramids which can adopt two distinct mirror-related configurations. Ordering of chains with a different configuration provides an extra level of structure complexity. Above T ≈ 750 K for Pb2Ba2BiFe5O13 and T ≈ 400 K for Pb(1.5)Ba(2.5)Bi2Fe6O16 the chains have a disordered arrangement. On cooling, a second-order structural phase transition to the ordered state occurs in both compounds. Symmetry changes upon phase transition are analyzed using a combination of superspace crystallography and group theory approach. Correlations between the chain ordering pattern and octahedral tilting in the perovskite blocks are discussed. Pb2Ba2BiFe5O13 and Pb(1.5)Ba(2.5)Bi2Fe6O16 undergo a transition into an antiferromagnetically (AFM) ordered state, which is characterized by a G-type AFM ordering of the Fe magnetic moments within the perovskite blocks. The AFM perovskite blocks are stacked along the CS planes producing alternating FM and AFM-aligned Fe-Fe pairs. In spite of the apparent frustration of the magnetic coupling between the perovskite blocks, all n = 4, 5, 6 A(n)Fe(n)O(3n-2) (A = Pb, Bi, Ba) feature robust antiferromagnetism with similar Néel temperatures of 623-632 K.

{110}-Layered B-cation ordering in the anion-deficient perovskite Pb2.4Ba2.6Fe2Sc2TiO13 with the crystallographic shear structure.

A novel anion-deficient perovskite-based compound, Pb(2.4)Ba(2.6)Fe(2)Sc(2)TiO(13), was synthesized via the citrate-based route. This compound is an n = 5 member of the AnBnO(3n-2) homologous series with unit-cell parameters related to the perovskite subcell a(p)≈ 4.0 Å as a(p)√2 ×a(p)× 5a(p)√2. The crystal structure of Pb(2.4)Ba(2.6)Fe(2)Sc(2)TiO(13) consists of quasi-2D perovskite blocks with a thickness of three octahedral layers separated by the 1/2[110](1[combining macron]01)(p) crystallographic shear (CS) planes, which are parallel to the {110} plane of the perovskite subcell. The CS planes transform the corner-sharing octahedra into chains of edge-sharing distorted tetragonal pyramids. Using a combination of neutron powder diffraction, (57)Fe Mössbauer spectroscopy and atomic resolution electron energy-loss spectroscopy we demonstrate that the B-cations in Pb(2.4)Ba(2.6)Fe(2)Sc(2)TiO(13) are ordered along the {110} perovskite layers with Fe(3+) in distorted tetragonal pyramids along the CS planes, Ti(4+) preferentially in the central octahedra of the perovskite blocks and Sc(3+) in the outer octahedra of the perovskite blocks. Magnetic susceptibility and Mössbauer spectroscopy indicate a broadened magnetic transition around T(N)∼ 45 K and the onset of local magnetic fields at low temperatures. The magnetic order is probably reminiscent of that in other AnBnO(3n-2) homologues, where G-type AFM order within the perovskite blocks has been observed.

An unusual high-spin ground state of Co3+ in octahedral coordination in brownmillerite-type cobalt oxide.

The crystal and magnetic structures of brownmillerite-like Sr(2)Co(1.2)Ga(0.8)O(5) with a stable Co(3+) oxidation state at both octahedral and tetrahedral sites are refined using neutron powder diffraction data collected at 2 K (S.G. Icmm, a = 5.6148(6) Å, b = 15.702(2) Å, c = 5.4543(6) Å; R(wp) = 0.0339, R(p) = 0.0443, χ(2) = 0.775). The very large tetragonal distortion of CoO(6) octahedra (1.9591(4) Å for Co-O(eq) and 2.257(6) Å for Co-O(ax)) could be beneficial for the stabilization of the long-sought intermediate-spin state of Co(3+) in perovskite-type oxides. However, the large magnetic moment of octahedral Co(3+) (3.82(7)µ(B)) indicates the conventional high-spin state of Co(3+) ions, which is further supported by the results of a combined theoretical and experimental soft X-ray absorption spectroscopy study at the Co-L(2,3) edges on Sr(2)Co(1.2)Ga(0.8)O(5). A high-spin ground state of Co(3+) in Sr(2)Co(1.2)Ga(0.8)O(5) resulted in much lower in comparison with a LaCoO(3) linear thermal expansion coefficient of 13.1 ppm K(-1) (298-1073 K) determined from high-temperature X-ray powder diffraction data collected in air.