Ca2CoNbO6: A new monoclinically distorted double perovskite

The new Ca₂CoNbO₆ double perovskites has been synthesized by solid-state reaction and its crystal structure has been refined using X-ray powder diffraction data. Rietveld fit to the diffraction data shows that the compound is monoclinically distorted and adopts space group P21/n. The cell parameters are: a = 5.4797(1) Å, b = 5.6051(1) Å, c = 7.8119(2) Å, β = 89.96(1)°. The Co and Nb are found to be distributed over the six coordinated octahedral sites in rock salt arrangement. However, nearly identical ionic radii of Co and Nb lead to severe degree of anti-site disorder (31%). The refined Co–O and Nb–O bond lengths are 1.9788(2) Å and 2.0642(2) Å respectively.     

LaSrMnCoO6: a new cubic double perovskite oxide

Single-phase polycrystalline powder samples of the double perovskite oxide LaSrMnCoO₆ were synthesized by the Pechini (citrate-gel) technique. The structural, magnetic and electrical properties of the obtained powders were investigated by X-ray diffraction, electron microscopy, dc magnetization, ac susceptibility and dc resistivity measurements. The crystal structure of the new compound was found to be cubic of space group at room temperature. Below 225 K, the samples exhibit ferrimagnetic behavior with a spin-glass-like character. Resistivity measurements indicate semiconducting behavior with two different conductivity mechanisms: thermally activated behavior below 190 K and variable range hopping above 190 K.     

Molecular hexagonal perovskite: a new type of organic-inorganic hybrid conductor

An organic charge-transfer (CT) salt (BEDT-TTF)₃(MnCl₃)₂(C₂H₅OH)₂ has been synthesized by a standard electrochemical method. The crystal data are monoclinic, C2/c (#15), a=38.863(4)Å, b=6.716(1) Å, c=23.608(3) Å, β=115.007(3)°, V=5584(1) Å³, and Z=4. The structure consists of one-dimensional (1D) infinite {[MnCl₃]⁻}_∞ magnetic chains and two-dimensional (2D) organic conduction pathways. The former consists of face-sharing octahedra of manganese chloride complex ions, and dominates the magnetic properties of this compound. Such a feature of the crystal structure closely relates to transition metal hexagonal perovskite compounds, all of which are known for frustrated triangular lattices comprised of weakly interacting 1D magnetic chains. The new compound exhibits a high conductivity down to 4 K.     

Electronic energy band structure of the double perovskite Ba2MnWO6

The electronic and magnetic structures of the double perovskite oxide Ba 2MnWO6 (BMW) were determined by employing the density functional theory within the generalized gradient approximation (GGA) + U approach. BMW is considered a prototype double perovskite due to its high degree of B-site ordering and is a good case study for making a comparison between computations and experiments. By adjusting the U-parameter, the electronic energy band structure and magnetic properties, which were consistent with the experimental results, were obtained. These computations revealed that the valence bands are mainly formed from Mn 3d and O 2p states, while the conduction bands are derived from W 5d and O 2p states. The localized bands composed from Mn 3d states are located in the bandgap. The results imply that the formation of polarons in the conduction band initiate the resonance Raman modes observed as a series of equidistant peaks.     

Cobalt diphosphonate with a new double chain structure exhibiting field-induced magnetic transition

A cobalt diphosphonate Co(H(2)O){C(5)H(5)N-CH(2)CH(OH)(PO(3))(PO(3)H)} (1) has been synthesized under hydrothermal conditions. It shows a novel type of double chain structure in which one of the two CPO(3) terminus caps on top of the {Co(2)(micro-O)2} dimer while the other connects the adjacent {Co(2)(micro-O)2} dimers into a chain. The magnetization measurements reveal that dominant antiferromagnetic interactions are mediated between the magnetic centers and the compound experiences a field-induced magnetic transition at low temperature with H(c) of ca. 15 kOe at 1.8 K.     

Alloying a single and a double perovskite: a Cu+/2+ mixed-valence layered halide perovskite with strong optical absorption

Introducing heterovalent cations at the octahedral sites of halide perovskites can substantially change their optoelectronic properties. Yet, in most cases, only small amounts of such metals can be incorporated as impurities into the three-dimensional lattice. Here, we exploit the greater structural flexibility of the two-dimensional (2D) perovskite framework to place three distinct stoichiometric cations in the octahedral sites. The new layered perovskites A^I₄[Cu^II(Cu^IIn^III)_0.5Cl₈] (1, A = organic cation) may be derived from a Cu^I–In^III double perovskite by replacing half of the octahedral metal sites with Cu²⁺. Electron paramagnetic resonance and X-ray absorption spectroscopy confirm the presence of Cu²⁺ in 1. Crystallographic studies demonstrate that 1 represents an averaging of the Cu^I–In^III double perovskite and Cu^II single perovskite structures. However, whereas the highly insulating Cu^I–In^III and Cu^II perovskites are colorless and yellow, respectively, 1 is black, with substantially higher electronic conductivity than that of either endmember. We trace these emergent properties in 1 to intervalence charge transfer between the mixed-valence Cu centers. We further propose a tiling model to describe how the Cu⁺, Cu²⁺, and In³⁺ coordination spheres can pack most favorably into a 2D perovskite lattice, which explains the unusual 1 : 2 : 1 ratio of these cations found in 1. Magnetic susceptibility data of 1 further corroborate this packing model. The emergence of enhanced visible light absorption and electronic conductivity in 1 demonstrates the importance of devising strategies for increasing the compositional complexity of halide perovskites.

A novel 2D halide perovskite with stoichiometric quantities of Cu⁺, Cu²⁺, and In³⁺ in the inorganic slabs shows emergent properties not seen in Cu^II or Cu^I–In^III perovskites, including enhanced visible-light absorption and electronic conductivity.     

Dielectric relaxation in a new double perovskite oxide Ho2MgZrO6

A new double perovskite oxide holmium magnesium zirconate Ho₂MgZrO₆ (HMZ) was prepared by solid state reaction technique. The crystal structure has been determined by powder X-ray diffraction which shows monoclinic phase at room temperature with cell parameters a = 9.3028 ± 0.0030 Å, b = 5.2293 ± 0.0008 Å, c = 4.4009 ± 0.0009 Å, β = 103.3746 ± 0.0166°. An analysis of complex permittivity with frequency was carried out assuming a distribution of relaxation times. The frequency dependent electrical data are analyzed in the framework of conductivity and electric modulus formalisms. At the high temperature range, conductivity data satisfy the variable range hopping (VRH) model. In this regime, the conductivity of sample obeys Mott’s T^1/4 law, characteristic of VRH. High temperature data indicates the formation of thermally activated small polarons. The scaling behaviour of imaginary part of electric modulus suggests that the relaxation describes the same mechanism at various temperatures.     

X-ray scintillation in lead-free double perovskite crystals

Metal halide perovskites have shown great performance for various applications,including solar cells,light emitting diodes,and radiation detectors,but they still suffer from the toxicity of lead and instability.Here we report the use of lanthanide series as trivalent metals to obtain low toxicity and highly stable double perovskites(Cs_2NaLnCl_6,Ln=Tb or Eu)with high scintillation light yield.The crystals exhibit typical f-f transitions of lanthanide cations,while Cs_2NaTbCl_6exhibits strong green photoluminescence,and Cs_2NaEuCl_6exhibits red photoluminescence.Under X-ray radiations,the light yield of Cs_2NaTbCl_6reaches46600 photons MeV~(-1),much higher than that of the commercially used(Lu,Y)_2SiO_5:Ce~(3+)crystals(LYSO,28500 photons MeV~(-1)),and previously reported lead-based perovskites(14000 photons MeV~(-1)).As a new member of lead-free perovskites,lanthanide-based double perovskites open up a new route toward radiation detections and potential medical imaging.     

Crystal and magnetic structure of the double perovskite Sr2CoUO6: a neutron diffraction study

Sr2CoUO6 double perovskite has been prepared as a polycrystalline powder by solid-state reaction, in air. This material has been studied by X-ray, neutron powder diffraction (NPD) and magnetic measurements. At room temperature, the crystal structure is monoclinic, space group P2(1)/n, Z= 2, with a= 5.7916(2), b= 5.8034(2), c= 8.1790(3) A, beta= 90.1455(6)degrees. The perovskite lattice consists of a completely ordered array of CoO6 and UO6 octahedra, which exhibit an average tilting angle phi= 11.4 degrees. Magnetic and neutron diffraction measurements indicate an antiferromagnetic ordering below TN = 10 K. The low-temperature magnetic structure was determined by NPD, selected among the possible magnetic solutions compatible with the P2(1)/n space group, according with the group theory representation. The propagation vector is k= 0. A canted antiferromagnetic structure is observed below TN = 10 K, which remains stable down to 3 K, with an ordered magnetic moment of 2.44(7)mu(B) for Co2+ cations. The magnetic moment calculated from the Curie-Weiss law at high temperatures (5.22 mu(B)/f.u.) indicates that the orbital contribution is unquenched at high temperatures, which is consistent with high-spin Co2+((4)T(1g) ground state) in a quasi-regular octahedral environment. Magnetic and structural features are consistent with an electronic configuration Co2+[3d(7)]-U6+[Rn].     

Large ferroelectric polarization in the new double perovskite NaLaMnWO6 induced by non-polar instabilities

Based on density functional theory calculations and group theoretical analysis, we have studied NaLaMnWO(6) compound which has been recently synthesized [G. King, A. Wills and P. M. Woodward, Phys. Rev. B: Condens. Matter, 2009, 79, 224428] and belongs to the AA'BB'O(6) family of double perovskites. At low temperature, the structure has monoclinic P2(1) symmetry, with layered ordering of the Na and La ions and rocksalt ordering of Mn and W ions. The Mn atoms show an antiferromagnetic collinear spin ordering, and the compound has been reported as a potential multiferroic. By comparing the low symmetry structure with a parent phase of P4/nmm symmetry, two distortion modes are found dominant. They correspond to MnO(6) and WO(6) octahedron tilt modes, often found in many simple perovskites. While in the latter these common tilting instabilities yield non-polar phases, in NaLaMnWO(6) the additional presence of the A-A' cation ordering is sufficient to make these rigid unit modes a source of the ferroelectricity. Through a trilinear coupling with the two unstable tilting modes, a polar distortion is induced, although the system has no intrinsic polar instability. The calculated electric polarization resulting from this polar distortion is as large as ～16 μC cm(-2). Despite its secondary character, this polarization is coupled with the dominant tilting modes and its switching is bound to produce the switching of one of two tilts, enhancing in this way a possible interaction with the magnetic ordering. The transformation of common non-polar purely steric instabilities into sources of ferroelectricity through a controlled modification of the parent structure, as done here by the cation ordering, is a phenomenon to be further explored.     

A new type of layer structure defects in chiral smectics

Under a low frequency AC electric field applied to the S_A phase an apparently homogeneous planar structure is obtained which is in fact composed of a system of parallel stripes perpendicular to the smectic layers. This texture persists even in the S*_C phase. The stripes are explained as a contrast on elongated focal conics originating from undulations of smectic layers. Such undulations are formed as a consequence of a reduction in the smectic layer thickness due to the electroclinic effect. The deformation of smectic layers has been calculated on the basis of the elastic free energy associated with their deformation.     

Synthesis of double perovskite and quadruple perovskite nanocrystals through post-synthetic transformation reactions

Lead-free halide perovskite nanocrystals (NCs) represent a group of emerging materials which hold promise for various optical and optoelectronic applications. Exploring facile synthetic methods for such materials has been of great interest to not only fundamental research but also technological implementations. Herein, we report a fundamentally new method to access lead-free Bi-based double perovskite (DP) and quadruple perovskite (or layered double perovskite, LDP) NCs based on a post-synthetic transformation reaction of Cs₃BiX₆ (X = Cl, Br) zero-dimensional (0D) perovskite NCs under mild conditions. The produced NCs show good particle uniformity, high crystallinity, and comparable optical properties to the directly synthesized NCs. The relatively slow kinetics and stop-on-demand feature of the transformation reaction allow real-time composition–structure–property investigations of the reaction, thus elucidating a cation-alloyed intermediate-assisted transformation mechanism. Our study presented here demonstrates for the first time that post-synthetic transformation of 0D perovskite NCs can serve as a new route towards the synthesis of high-quality lead-free perovskite NCs, and provides valuable insights into the crystal structures, excitonic properties and their relationships of perovskite NCs.

Lead-free perovskite nanocrystals are synthesized by post-synthetic transformation reactions. The post-synthetic transformations show the structural flexibility of zero-dimensional perovskite nanocrystal materials.     

Non-collinear magnetic structure of the Sr2ErRuO6 double perovskite

The crystal and magnetic structure of Sr₂ErRuO₆ has been studied by means of neutron powder diffraction as well as magnetization and susceptibility measurements. Neutron diffraction profile measured at 50 K shows that the Ru⁵⁺ and Er³⁺ are ordered in the B-sites of the perovskite-type structure, while the Sr atoms occupy the A-site. This compound crystallizes with a monoclinic unit cell, space group P2₁/n and lattice parameters are approximately √2a_p × √2a_p × 2a_p. Magnetic susceptibility measurements reveal the existence of antiferromagnetic interactions in which Ru⁵⁺ and Er³⁺ sublattices are involved. The field dependence of the magnetization indicates the presence of a weak ferromagnetic component at the transition temperature, arising from the spin canting of the antiferromagnetically ordered Ru⁵⁺ and Er³⁺ moments. Thermal evolution of the neutron diffraction patterns indicate that the Nèel temperature is 36 K and the magnetic reflections can be indexed on the basis of a propagation vector k = [0, 0, 0]. The spin arrangement is described by the AxAz magnetic modes where the Ru⁵⁺ and Er³⁺ moments are mainly aligned along the c-axis of the structure, forming an angle of 6° with the c-axis in the case of the Er³⁺ sublattice and 15° for the Ru⁵⁺ moment.     

Synthesis and crystal structure of a Pb complex with ciprofloxacin

A hydrothermal reaction of ciprofloxacin with PbCl₂ · 2H₂O and Na₂S yields a metal complex [Pb₂(H-Cip)₆S]Cl₆ (I), which was characterized by elemental analysis, IR, and single crystal diffraction analyses. Complex I crystallizes in the rhombohedral system, space group $R\bar 3c$ , with lattice parameters a = 15.7800(7), c = 77.901(9) ?, V = 16799(2) ?³, Z = 12, ??_calcd = 1.646 mg/m³.     

A new type of stabilized carbonucleophiles with a carboranyl group

Palladium-catalyzed allylation of carboranylacetic esters gives C-allyl derivatives in high yield. Thus, a new type of stabilized carbonucleophiles with the electron-withdrawing o-carboranyl group has been made.