Crystal structure of Tl0.5Pb0.5Sr2Ca2Cu3O9 at 300 K and around Tc (118 K)

The crystal structure including the cation distribution, of a polycrystalline sample of nominal composition Tl_0.5Pb_0.5Sr₂Ca₂Cu₃O₉ with T_c = 118.2 K has been determined using resonant synchrotron X-ray diffraction data collected at the Cu K, Tl L_III and Sr K edges and time-of-flight powder neutron diffraction data. No oxygen deficiency was observed, but cation disorder at all the non copper sites according to the formula (Tl_0.60Pb_0.40)(Sr_1.60Ca_0.40)(Ca_1.93Tl_0.07) Cu₃O₉ gives a mean hole concentration of 0.18(1) per Cu atom for the three CuO₂ planes, consistent with the high T_c for this material. Analysis of five time-of-flight powder neutron diffraction data between 80 and 150 K have revealed a possible discontinuity in the variation of the c lattice parameter at T_c, due to an anomaly in the position of the apical oxygen atoms.     

Study of structural and electronic transport properties of Ce-doped LaMnO3

The structural and electronic transport properties of La_1−x Ce _x MnO₃ (x=0.0–1.0) have been studied. All the samples exhibit orthorhombic crystal symmetry and the unit cell volume decreases with Ce doping. They also make a metal-insulator transition (MIT) and transition temperature increases with increase in Ce concentration up to 50% doping. The system La_0.5Ce_0.5MnO₃ also exhibits MIT instead of charge-ordered state as observed in the hole doped systems of the same composition.     

Synthesis and characterization of two novel pyridine-containing framework gallium ethylenediphosphonates

Two novel gallium diphosphonates, (C₅H₅N)Ga₃F(O₃PC₂H₄PO₃)₂ (I) (triclinic, P-1, a=8.2880(12) Å, b=11.7197(16) Å, c=11.7601(17) Å, α=71.589(3)°, β=70.577(3)°, γ=77.313(3)°, V=1013.7(2) Å³, Z=2, R₁=0.0352, wR₂=0.0980) and (C₅H₅NH)₂[Ga₄F₂(O₃PC₂H₄PO₃)₃] (II) (triclinic, P-1, a=8.670(4) Å, b=9.742(3) Å, c=10.406(2) Å, α=81.44(3)°, β=65.83(5)°, γ=67.16(3)°, V=739.0(4) Å³, Z=2, R₁=0.0600, wR₂=0.1495) have been synthesised by solvothermal methods in the presence of pyridine and their structures determined using single-crystal X-ray diffraction data. Both compounds I and II are composed of various Ga-centered polyhedra and ethylenediphosphonate groups that link together to form framework materials with one- and two-dimensional channel systems, respectively. The two structures are formed in the presence of structure-directing pyridine molecules that are directly bound to some of the Ga atoms in I, and are protonated as pyridinium cations in II. Compounds I has a charge-neutral framework, while compound II has an anionic framework. Both materials provide rare examples of organically structure-directed framework metal diphosphonate materials.     

Rational design of the pore system within the framework aluminium alkylenediphosphonate series

We report here on the solvothermal synthesis and crystal structure of the hybrid organic-inorganic framework material Al(2)[O(3)PC(3)H(6)PO(3)](H(2)O)(2)F(2).H(2)O (orthorhombic, Pmmn, a = 12.0591(2) A, b = 19.1647(5) A, c = 4.91142(7) A, Z = 4), the second member of the Al(2)[O(3)PC(n)H(2n)PO(3)](H(2)O)(2)F(2).H(2)O series. The structure consists of corrugated chains of corner-sharing AlO(4)F(2) octahedra in which alternating AlO(4)F(2) octahedra contain two fluorine atoms in a trans or a cis configuration. The diphosphonate groups link the chains together through Al-O-P-O-Al bridges and through the propylene groups to form a three-dimensional framework structure containing a one-dimensional channel system. The linkage of the corrugated inorganic Al-O-P layers within the structure results in the formation of two types of channel that differ in size, shape and composition. The smaller channel is unoccupied; the larger channel is more elongated and contains two extra-framework water molecules per unit cell. A computational investigation into the driving force that controls the stacking arrangement of the Al-O-P inorganic layers within this series of compounds reveals that the stacking is found to be controlled by thermodynamic factors, arising chiefly from the conformation of the organic linker molecule used to connect the inorganic sheets. It is found that the registration of the inorganic layers can be engineered by selecting an appropriate, simple organic spacer or linker alkyl chain, where an even number of carbon atoms in the alkyl chain directs formation of aligned, stacked, inorganic sheets (AAAAAA), and an odd number directs formation of unaligned, stacked sheets (ABABAB) and the formation of one or two channel types in the resultant structure, respectively. This combination of alkyl-chain linkers in conjunction with corrugated inorganic layers is an effective tool to rationally design the pore system of hybrid framework materials.     

Studies of microstructure and ruthenium valence in the ruthenocuprates Pb2RuSr2Cu2O8Cl and (Ru, M)Sr2GdCu2O8 (M=Sn, Nb)

Ruthenocuprate microstructures and Ru valences have been studied. Electron microscopy reveals short-range order of the RuO₆ octahedra rotations into a √2a×√2a×c supercell in Pb₂RuSr₂Cu₂O₈Cl. However, reanalysis of neutron diffraction data gives no significant difference between the populations of the rotation states, showing that the coherence length is very short (<100 Å). The Ru valence estimated from the XANES spectrum of Pb₂RuSr₂Cu₂O₈Cl is ∼5, in keeping with the physical properties of this material which show that there is essentially no Ru-Cu charge transfer. The Ru valence in doped Ru_1−xM_xSr₂GdCu₂O₈ (M=Sn, Nb) is ∼4.8 in all samples, verifying a previous rigid band analysis of the charge distribution in these materials.     

Microstrain sensitivity of orbital and electronic phase separation in SrCrO3

An orbital ordering transition and electronic phase coexistence have been discovered in SrCrO3. This cubic, orbitally-degenerate perovskite transforms to a tetragonal phase with partial orbital order. The tetragonal phase is antiferromagnetic below 35-40 K, whereas the cubic phase remains paramagnetic at low temperatures. The orbital ordering temperature (35-70 K) and coexistence of the two electronic phases are very sensitive to lattice strain. X-ray measurements show a preferential conversion of the most strained regions in the cubic phase. This reveals that small fluctuations in microstrain are sufficient to drive long range separation of competing electronic phases even in undoped cubic oxides.     

Large Magnetization and Frustration Switching of Magnetoresistance in the Double‐Perovskite Ferrimagnet Mn2FeReO6

Ferrimagnetic A₂BB′O₆ double perovskites, such as Sr₂FeMoO₆, are important spin‐polarized conductors. Introducing transition metals at the A‐sites offers new possibilities to increase magnetization and tune magnetoresistance. Herein we report a ferrimagnetic double perovskite, Mn₂FeReO₆, synthesized at high pressure which has a high Curie temperature of 520 K and magnetizations of up to 5.0 μ_B which greatly exceed those for other double perovskite ferrimagnets. A novel switching transition is discovered at 75 K where magnetoresistance changes from conventional negative tunneling behavior to large positive values, up to 265 % at 7 T and 20 K. Neutron diffraction shows that the switch is driven by magnetic frustration from antiferromagnetic Mn²⁺ spin ordering which cants Fe³⁺ and Re⁵⁺ spins and reduces spin‐polarization. Ferrimagnetic double perovskites based on A‐site Mn²⁺ thus offer new opportunities to enhance magnetization and control magnetoresistance in spintronic materials.