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Multiferroics, showing the coexistence of two or more ferroic orderings at room temperature, could harness a revolution in multifunctional devices. However, most of the multiferroic compounds known to date are not magnetically and electrically ordered at ambient conditions, so the discovery of new materials is pivotal to allow the development of the field. In this work, we show that BaFe

By means of single-crystal X-ray diffraction, we give direct crystallographic evidence of a centrosymmetry breaking below TS = 200 K, concomitant with the onset of a commensurate structural modulation in the quadruple perovskite YMn3Mn4O12. This result, which explains the anomalously large thermal coefficient of the Y3+ ion in previously reported structural models, is attributed to the small size of the Y3+ ion, which causes its underbonding within the dodecahedral coordination polyhedron. The present data are consistent with a commensurate superstructure described by an I-centered pseudo-orthorhombic cell with polar Ia symmetry and a ? aF?2 = 10.4352(7) Å, b ? 2bF = 14.6049(9) Å, c ? cF?2 = 10.6961(7) Å, and ? = 90.110(3)°, where aF ? cF ? 7.45 Å, bF ? 7.34 Å, and ? ? 91° are the unit cell parameters of the I2/m structure observed at room temperature. Consistent with the above polar structure, at lower temperature, T* = 70 K, we observe in polycrystalline samples an anomaly of the direct current (DC) and alternating current (AC) magnetization, concomitant with the appearance of a net electric polarization, as indicated by pyrocurrent and dielectric constant measurements. These results, complemented by electrical transport measurements, suggest a magnetic ferroelectricity driven by short-range magnetic order in YMn3Mn4O12.

A novel chloro-substituted zinc-phosphate, (C8N2H20)[ZnCl(PO3(OH))], has been synthesized by a slow evaporation method in the presence of 1,3-cyclohexanebis- (methylamine), which acts as a template. The structure consists of vertex linked ZnO3Cl and PO3(OH) tetrahedral, assembled into corrugated porous layers [ZnCl(PO3(OH))2]∞ with (4.82) topology. The optical properties were also investigated using Diffuse Reflecting Spectroscopy (DRS), showing that the title compound has semiconducting properties. In addition, the catalytic activity of (C8N2H20)[ZnCl(PO3(OH))]2 has been tested in the acetalisation reaction of aldehydes. The title compound displayed a high catalytic activity with practically total conversion in many examples using MeOD as solvent and as the sole source of acetalisation. More importantly, the reaction crudes are very clean and only the preferred products are found in the NMR spectra., R. P. H. and I. A. thank the Spanish Ministerio de Economía, Industria y Competitividad (MINECO-FEDER CTQ2017-88091-P and PGC2018-093451-B-I00) and Diputación General de Aragón (DGA) (Research Groups E07_17R and E17_17R) for financial support of their research.

A P21/c synthetic (Ca0.2Co0.8)CoSi2O6 pyroxene was synthesized by slow cooling from melt at high pressure. Single crystals suitable for X-ray diffraction were obtained and refined. The results were compared to those of C2/c pyroxenes along the series CaCoSi2O6–Co2Si2O6. Strong similarities in the crystal chemical mechanism of the transition with the synthetic CaFeSi2O6–Fe2Si2O6 and CaMgSi2O6–Mg2Si2O6 pyroxenes, both at an average and local level are apparent.The results, examined together with two new refinements of pigeonite in the ureilites ALHA77257 and RKPA80239 and with a set of natural and synthetic C2/c and P21/c pyroxenes, show that the average cation radius in the M2 site is the driving force for the phase transition from C2/c to P21/c. The longest M2–O3 distances and the O3–O3–O3 angles follow the same trend, dictated only by the ionic radius in M2, in either synthetic or natural pyroxenes, regardless of the ionic radius of the M1 cations. The transition also affects the difference between bridging and non-bridging oxygen atoms and the extent of tetrahedral deformation, whereas the M1–O, M2–O1 and M2–O2 distances are unaffected by the transition and are determined only by the ionic radius of the bonding cation. The structural changes between the ionic radius and the high temperature C2/c and P21/c transitions are similar, and different to the high-pressure transition.Analysis of natural and synthetic pyroxenes shows that the transition with composition occurs in strain free pyroxenes for a critical radius of 0.85 Å. Increasing strain stabilizes the P21/c structure to a higher temperature and larger cation radius.Finally, our results show that the monoclinic P21/c Ca-poor clinopyroxene, i.e the mineral pigeonite, crystallizes only at conditions where the structure is HT-C2/c, and changes to the P21/c symmetry during cooling.

The organic–inorganic hybrid non-centrosymmetric material [(C 2 H 5 ) 4 N] 2 ZnI 3.86 Cl 0.14 has been studied by X-ray diffraction (XRD), differential scanning calorimetry (DSC), dielectric and transport measurements. In analogy with the corresponding tetraiodo-zincate analogue, the material crystallizes at room temperature in the tetragonal system, space group P 4 2 1 m (No. 113), with lattice parameters a = 13.743(6) and c = 14.785(10) A. DSC and XRD characterizations pointed out the occurrence of two phases transitions, one of second order at about 290 K and the other of the first order at T = 451 K. The former is related to an electrical transition from insulating to thermally activated transport mechanism displaying clear hints of ionic conduction, the latter leads to a phase showing the typical features of plastic crystals in its powder XRD pattern. The pattern was indexed by an orthorhombic cell, a = 15.724(1), b = 17.907(1) and c = 10.585(1) A, and a reliable model was found and refined in the Pna2 1 space group. The model consists of ordered tetrahedral ZnCl 4 2− units intercalated by fully disordered tetraethylammonium cations.

A comprehensive study by high-resolution transmission electron microscopy (TEM) and X-ray diffraction (XRD) was carried out on Ga2O3 epilayers grown at low temperature (650 °C) by vapor phase epitaxy in order to investigate the real structure at the nanoscale. Initial XRD measurements showed that the films were of the so-called e phase; i.e. they exhibited hexagonal P63mc space group symmetry, characterized by disordered and partial occupation of the Ga sites. This work clarifies the crystal structure of Ga2O3 layers deposited at low temperature at the nanoscale: TEM investigation demonstrates that the Ga atoms and vacancies are not randomly distributed, but actually possess ordering, with (110)-twinned domains of 5–10 nm size. Each domain has orthorhombic structure with Pna21 space group symmetry, referred to as κ-Ga2O3. Further XRD analysis carried out on thicker samples (9–10 μm) confirmed this finding and provided refined structural parameters. The six (110)-type twinned ordered domains together – if the domain size falls below the actual resolution of the probing techniques – can be misinterpreted as the disordered structure with its P63mc space group symmetry usually referred to as e-Ga2O3 in the current literature. The crystal structure of these Ga2O3 layers consists of an ABAC oxygen close-packed stacking, where Ga atoms occupy octahedral and tetrahedral sites in between, forming two types of polyhedral layers parallel to (001). The edge-sharing octahedra and the corner-sharing tetrahedra form zig-zag ribbons along the [100] direction. Anti-phase boundaries are common inside the domains. The polar character of the structure is confirmed, in agreement with the characteristics of the Pna21 space group and previous observations.

By means of single-crystal X-ray diffraction, we give direct crystallographic evidence of a centrosymmetry breaking below

The crystal structure of 4-fluoro­benzyl­ammonium di­hydrogen phosphate, [FC6H4CH2NH3]H2PO4, consists of layers of 4-fluoro­benzyl­ammonium cations and di­hydrogen phosphate anions that alternate along the c axis, connected by hydrogen bonds into a three-dimensional network., The asymmetric unit of the title salt, [p-FC6H4CH2NH3]+·H2PO4 −, contains one 4-fluoro­benzyl­ammonium cation and one di­hydrogen phosphate anion. In the crystal, the H2PO4 − anions are linked by O—H⋯O hydrogen bonds to build corrugated layers extending parallel to the ab plane. The FC6H4CH2NH3 + cations lie between these anionic layers to maximize the electrostatic inter­actions and are linked to the H2PO4 − anions through N—H⋯O hydrogen bonds, forming a three-dimensional supra­molecular network. Two hydrogen atoms belonging to the di­hydrogen phosphate anion are statistically occupied due to disorder along the OH⋯HO direction.

The chemical and physical properties of the double perovskite Pb2FeMoO6 are systematically studied by means of structural and magnetic characterization. The compound crystallizes in the cubic Fm3¯m space group, with partial cation order involving iron and molybdenum at the perovskite B site. Structural and Mössbauer characterization points to the presence of nanometer-sized antiphase domains within the ordered matrix giving rise to two iron populations, characterized by different chemical environments, with the same weight but different valence (0.3 electrons) and inequivalent magnetic anisotropy. This structural feature deeply affects the properties of the compound: Mössbauer and EPR measurements show a high-temperature superparamagnetic-like behavior ascribed to weak magnetic interactions occurring between the antiphase domains and the rest of the sample. However, below 270 K ferrimagnetic ordering of the atomic moments is observed by neutron diffraction and SQUID magnetometry, with the onset of blocked long range magnetic interactions on the Mössbauer timescale involving both the antiphase domains and the ordered matrix below 230 K. The superparamagnetic-like behavior is ascribed to the presence of low anisotropy barriers, giving rise to an extremely thin hysteresis loop at 5 K, with a very small coercive field and remnant magnetization. The observed saturation magnetization of 1.75 µB per f.u. is in agreement with the magnetic structure determined by neutron diffraction, with the two symmetry independent sites producing a ferrimagnetic resultant µS = 1.59 µB.

We investigate the specific influence of structural disorder on the suppression of antiferromagnetic order and on the emergence of cuprate superconductivity. We single out pure disorder, by focusing on a series of Y$_{z}$Eu$_{1-z}$Ba$_2$Cu$_3$O$_{6+y}$ samples at fixed oxygen content $y=0.35$, in the range $0\le z\le 1$. The gradual Y/Eu isovalent substitution smoothly drives the system through the Mott-insulator to superconductor transition from a full antiferromagnet with N\'eel transition $T_N=320$ K at $z=0$ to a bulk superconductor with superconducting critical temperature $T_c=18$ K at $z=1$, YBa$_2$Cu$_3$O$_{6.35}$. The electronic properties are finely tuned by gradual lattice deformations induced by the different cationic radii of the two lanthanides, inducing a continuous change of the basal Cu(1)-O chain length, as well as a controlled amount of disorder in the active Cu(2)O$_2$ bilayers. We check that internal charge transfer from the basal to the active plane is entirely responsible for the doping of the latter and we show that superconductivity emerges with orthorhombicity. By comparing transition temperatures with those of the isoelectronic clean system we deterime the influence of pure structural disorder connected with the Y/Eu alloy., Comment: 10 pages 11 figures, submitted to Journal of Physics: Condensed Matter, Special Issue in memory of Prof. Sandro Massida

(C8H12NO)(2)[ZnCl4] is an interesting ferroelectric organic-inorganic hybrid compound that shows a complex structural phase diagram, investigated in this work by X-ray diffraction and differential scanning calorimetry, characterized by an irreversible transition occurring on heating at 390 K, and coupled with successive transformations taking place on cooling in a metastable regime. The basic structural transition, leading from a monoclinic P2(1) to an orthorhombic P2(1)2(1)2(1) symmetry and involving the doubling of the unit cell volume, is associated with an order-disorder transformation of the 4-methoxybenzylammonium cations coupled with a reorientation of tetrachloridozincate anions. During cooling, the cationic order and the monoclinic symmetry are progressively restored, but the doubling of the original cell volume is maintained by the alternate canting of adjacent cationic layers. It is noteworthy that all the polymorphs preserve the non-centric nature of the structure, but the ferroelectric behavior, characterized by high saturation polarization P-S = 17 mu C cm(-2) and relatively low coercive field E-C = 8 kV cm(-1), is lost in the transition on heating and not recovered at low temperature when the original polar P2(1) symmetry is restored.

A redetermination of the crystal structure of minodronic acid monohydrate was carried out in order to provide accurate atomic coordinates and geometry information, whose knowledge is fundamental to elucidate the presumed polymorphism of the compound at room temperature., In a previous study, the X-ray structure of the title compound, C9H12N2O7P2·H2O, was reported [Takeuchi et al., (1998 ▸). Chem. Pharm. Bull. 46, 1703–1709], but neither atomic coordinates nor details of the geometry were published. The structure has been redetermined with high precision as its detailed knowledge is essential to elucidate the presumed polymorphism of minodronic acid monohydrate at room temperature. The mol­ecule crystallizes in a zwitterionic form with cationic imidazolium[1,2a]pyridine and anionic phospho­nate groups. The dihedral angle formed by the planes of the pyridine and imidazole rings is 3.55 (9)°. A short intra­molecular C—H⋯O contact is present. In the crystal, mol­ecules are linked by O—H⋯O, N—H⋯O and C—H⋯O hydrogen bonds and π–π inter­actions [centroid-to-centroid distance = 3.5822 (11) Å], forming a three-dimensional structure.

In this study, we show how the combination of metal ions, counter-anions and opportunely functionalized and preorganized ligands gives rise to two distinct supramolecular isomers, coordination polymeric chains and hexameric macrocycles. The hexamers then aggregate to form a cubic structure exhibiting permanent microporosity. The supramolecular assemblies are formed with Ag(+), thioether functionalized bis(pirazolyl)methane ligands and CF3SO3(-)/PF6(-) as the counter-anions. Five different ligands were prepared by modifying the peripheral thioether moiety with naphthyl, methoxy, m-Me, p-Me and F groups (L(SNf), L(SPhOMe), L(SPhm-Me), L(SPhp-Me), and L(SPhF)). Helicoidal coordination polymeric chains are formed with CF3SO3(-) (general formula [Ag(L)]n(CF3SO3)n), whereas macrocyclic hexamers are formed with PF6(-) (general formula [Ag(L)]6(PF6)6). The macrocycles self-assemble into ordered capsules with the shape of a tetrahedron, and the overall framework is sustained by Ag(+)···(PF6(-))···Ag(+) contacts. The capsules generate a highly symmetric structural arrangement, which is characterized by permanent microporosity arising from two distinct types of microporous chambers in the structure. The gas absorption isotherms show that the materials can selectively adsorb CO2 and N2O over CH4 and N2. The modulation of the microporosity of the materials is achieved by the different thioether functionalization of the ligands L(SNf), L(SPhOMe), L(SPhm-Me), and L(SPhF). The diffusion and localization of the gas molecules within the cavities were investigated by 2D (1)H-(13)C solid state NMR on samples loaded with enriched (13)CO2, showing that both types of cavities are accessible to guest molecules from the gas phase.

The commensurate crystal structure of the magnetic phase occurring below 7 K of the multiferroic Pb2MnWO6 perovskite has been solved by the introduction of the superspace approach. This lead based double perovskite is characterized by a complex ferrielectric non-centrosymmetric nuclear structure with orthorhombic symmetry stable in a wide temperature range. As indicated from the analysis of powder neutron diffraction data, the low temperature antiferromagnetic structure showing a propagation vector k 1/4 [1/4 0 0] is stabilized by a multi-step process involving the evolution from incommensurate to commensurate spin ordering with a concomitant change of the magnetic symmetry. The determination of the Pb2MnWO6 magnetic structure offers a meaningful example of the superspace application and provides a detailed phase diagram of the involved magnetic states. Nowadays this ordered perovskite could be considered as a new type of multiferroic material combining ferrielectric properties and a long period antiferromagnetic structure.

The synthesis and structural and magnetic characterizations of K3Fe6F19, a new iron potassium fluoride with a complex tungsten bronze related structure, are presented. This phase was found during the investigation of relatively low-temperature (600 degrees C) synthesis conditions of classical tetragonal tungsten bronze (TTB) fluorides and can be considered an intermediate that forms at this temperature owing to faster crystallization kinetics. The K3Fe6F19 compound has an orthorhombic structure (space group Cmcm (63), a = 7.6975(3) angstrom, b = 18.2843(7) angstrom, c = 22.0603(9) angstrom) related to the TTB one, where the perovskite cage is substituted by a large S-shaped channel simultaneously occupied by two potassium atoms. The magnetic structure, characterized by magnetization measurements on an oriented single crystal and powder neutron diffraction, is dominated by the presence of interconnected double stripes of antiferromagnetic triangular exchange interaction patterns alternately rotated in clock- and anticlockwise fashion. The magnetic order takes place in a wide temperature range, by increasing progressively the interaction dimensionality.

The crystal structure and ferroelectric properties of ε-Ga

The crystal structure and ferroelectric properties of epsilon-Ga2O3 deposited by low-temperature MOCVD on (0001) sapphire were investigated by single-crystal X-ray diffraction and the dynamic hysteresis measurement technique. A thorough investigation of this relatively unknown polymorph of Ga2O3 showed that it is composed of layers of both octahedrally and tetrahedrally coordinated Ga3+ sites, which appear to be occupied with a 66% probability. The refinement of the crystal structure in the noncentrosymmetric space group P6(3)mc pointed out the presence of uncompensated electrical dipoles suggesting ferroelectric properties, which were finally demonstrated by independent measurements of the ferroelectric hysteresis. A clear epitaxial relation is observed with respect to the c-oriented sapphire substrate, with the Ga2O3 [10-10] direction being parallel to the Al2O3 direction [11-20], yielding a lattice mismatch of about 4.1%.

The physical characterization and the extended crystallographic study of the double perovskite system Pb2Mn0.6Co0.4WO6 indicate an improper ferroelectric contribution to the polarization induced by the magnetic ordering. In the paramagnetic phase, the compound displays a centrosymmetric orthorhombic double perovskite structure with the Pmcn1' symmetry. The structure is strongly distorted by the lead stereoactivity. Magnetization measurements show two magnetic transitions at 188 and 9 K, but the time-of-flight neutron diffraction data provide evidence for a long-range magnetic ordering only below the second transition. Quantitative structure refinements combined with a comprehensive symmetry analysis indicate the Pm'c2(1)' magnetic space group to be the adequate symmetry to describe the structural distortions and spin ordering in the ground state of the system. The symmetry implies a coexistence of a spontaneous ferromagnetic moment and a ferroelectric polarization along the orthogonal b- and c-axes, respectively, in the long-range ordered structure. Macroscopic measurements confirm the presence of the spontaneous polarization also below the first transition at 188 K, where only short-range magnetic correlations are evidenced by diffuse scattering in neutron diffraction.

We present a comprehensive study of the electrical properties of bulk polycrystalline BiFe0.5Mn0.5O3, a double perovskite synthesized in high-pressure and high-temperature conditions. BiFe0.5Mn0.5O3 shows an antiferromagnetic character with T-N = 288 K overlapped with an intrinsic antiferroelectricity due to the Be3+ stereochemical effect. Beyond this, the observation of a semiconductor insulator transition at T-p approximate to 140 K allows one to define three distinct temperature ranges with completely different electrical properties. For T > T-N, electric transport follows an ordinary thermally activated Arrhenius behavior; the system behaves as a paramagnetic semiconductor. At intermediate temperatures (T-p < T < T-N), electric transport is best described by Mott's variable range hopping model with lowered dimensionality D = 1, stabilized by the magnetic ordering process and driven by the inhomogeneity of the sample on the B site of the perovskite. Finally, for T < T-p, the material becomes a dielectric insulator, showing very unusual poling-induced soft ferroelectricity with high saturation polarization, similar to the parent compound BiFeO3. Under external electric poling, the system irreversibly evolves from antiferroelectric to polar arrangement.

Herein, we present the structural characterization of the core and surface of colloidally stable ultrathin bismuth sulfide (Bi(2)S(3)) nanowires using X-ray Absorption Spectroscopy (EXAFS and XANES), X-ray Photoelectron Spectroscopy (XPS), and Nuclear Magnetic Resonance (NMR). These three techniques allowed the conclusive structural characterization of the inorganic core as well as the coordination chemistry of the surface ligands of these structures, despite the absence of significant translational periodicity dictated by their ultrathin diameter (1.6 nm) and their polycrystallinity. The atomic structure of the inorganic core is analogous to bulk bismuthinite, but Bi atoms display a remarkably higher coordination number than in the bulk. This can be only explained by a model in which each bismuth atom at the surface (or in close proximity to it) is bound to at least one ligand at any time.

The crystal structure of the modulated, low-temperature martensitic phase in Ni2.41Fe0.59Ga ferromagnetic shape memory alloy (FSMA) has been determined by Rietveld refinement of neutron powder diffraction data. The structure shows an incommensurate modulated crystal lattice with some analogies with the 7 M modulated martensitic structure found in Ni2Mn1.2Ga0.8 Heusler alloy. The observed type of lattice modulation with q = 0.3521c∗ gives rise to a new type of martensitic crystal structure in the FSMAs.

Magnetic and structural properties in multifunctional FSMA (Ferromagnetic Shape Memory Alloys) belonging to Heusler family are frequently related to the occurrence of structural modulation in martensitic phases. The highest MFIS (Magnetic Field Induced Strain) effect has been observed in Ni-Mn-Ga alloys showing martensitic modulated structures. Depending on the composition, pressure and temperature conditions, this periodic structural distortion, consisting of shuffling of atomic layers along specific crystallographic directions, accompanies the martensitic transformation. Over the years, different modulated martensitic structures have been observed and classified depending upon the periodicity of corresponding superstructure (nM with n=3, 5, 6, 7, 12 etc). On the other hand, it has been demonstrated that in most cases such structural modulation is incommensurate and the crystal structure can be solved by applying superspace approach. The crystallographic representation of different modulated structures, obtained by structure refinement on powder diffraction data, suggests a unified description where every different “nM” periodicity can be straightforwardly represented. It will be presented an overview illustrating structural features of several displacive modulated martensitic lattices. For a specific Ni-Mn-Ga composition, the evolution of structural modulation upon temperature change will be illustrated.

For the first time, the 7M modulated structure, frequently observed in ferromagnetic shape memory Ni–Mn–Ga martensitic phases, is solved by powder diffraction analysis. Two polycrystalline samples with composition Ni2Mn1.2Ga0.8 and Ni2.15Mn0.85Ga, respectively, showing a 7M martensitic state stable at room temperature, were studied. The determination of the modulated crystal structure of Ni2Mn1.2Ga0.8 martensite was achieved by refining the X-ray powder diffraction pattern by the Rietveld method. The basic structure belongs to monoclinic symmetry. The crystal structure, solved within the superspace approach, is found to show an incommensurate 7M modulation with q = 0.308c∗. The Rietveld refinement for Ni2.15Mn0.85Ga martensite on the basis of neutron powder data surprisingly provides a very similar incommensurate 7M structure with the same periodicity and analogous modulation function. The incommensurate structure presents typical displacive modulation with several analogies with the Zhdanov (5, 2 ¯ )2 stacking sequence.

Focusing here on the effects of zinc doping in a nanocrystalline matrix of tin dioxide, inverse opal prototype sensors are presented and extensively studied as superior candidates for gas sensing applications. Courtesy of factors including controlled porosity, enhanced surface to volume ratio and homogeneous dispersion of species in the crystalline lattice assured by the sol-gel technique, prototype sensors were prepared with high dopant ratios in a range of new compositions. Exploiting their high sensitivities to low-gas concentrations at low working temperatures, and thanks to the presented templated sol-gel approach, the prepared sensors open up new frontiers in compositional control over the sensing oxide materials, consequently widening the possibilities available in on-demand gas sensor synthesis.

We report a comprehensive study of the spontaneous magnetization reversal (MRV) performed on the disordered polycrystalline perovskite BiFe(0.5)Mn(0.5)O(3), an intriguing compound synthesized in high pressure-high temperature conditions. In disordered systems, the origin of MRV is not completely clarified, yet. In BiFe(0.5)Mn(0.5)O(3), compositional disorder involves the ions on the B-site of the perovskite determining the presence of mesoscopic clusters, characterized by high concentrations of iron or manganese and thus by different resultant magnetization. This leads to the observation of two singular fields H(1) and H(2) dependent on the degree of inhomogeneity, unpredictably changing from sample to sample due to synthesis effects. These fields separate different magnetic responses of the system; for applied fields H H(1), the Fe and Mn clusters weakly interact in a competitive way, giving rise to MRV, while for an intermediate field regime the energy of this weak interaction becomes comparable to the energy of the system under field application. As a consequence, the zero field cooled magnetization thermal evolution depends on the sample degree of inhomogeneity. In this field regime, applied field Mössbauer spectroscopy indicates that the iron rich clusters are highly polarized by the field, while the largest part of the material, consisting of AFM clusters characterized by axial anisotropy and uncompensated moments, shows soft or hard magnetism depending on T. Above the higher singular field, the M(T) curves show the trend expected for a classical antiferromagnetic material and the competitive character is suppressed. The MRV phenomenon results to be highly sensitive on both the thermal and magnetic measurement conditions; for this reason the present work proposes a characterization strategy that in principle has a large applicability in the study of disordered perovskites showing similar phenomenology.

The effect of Zn substitution on a series of clinopyroxenes along the join CaZnSi2O6-Zn2Si2O6 was studied. The pyroxenes were synthesized at P = 4-5 GPa and T = 1000-1200 degrees C by a multi-anvil apparatus. SEM-EDS and XRD analysis showed complete solid solution; all of the samples have the C2/c space group. No miscibility gap between clino- and orthopyroxene nor phase transition to the P2(1)/c space group was found. Moreover, the cell volume of Ca-Zn pyroxenes decreases less than expected from the decrease of the average cation size for the substitution of Zn for Ca. The crystal structures of three synthetic pyroxenes of composition (Ca0.5Zn0.5)ZnSi2O6, (Ca0.3Zn0.7) ZnSi2O6, and (Ca0.2Zn0.8)ZnSi2O6 were refined by single-crystal X-ray diffraction (R-4 sigma between 3 and 4.5%). It was observed that the Ca-Zn substitution occurs in the M2 polyhedron, with a sub-site splitting of Zn in a position at approximately 0.7 angstrom from Ca. In this position, Zn retains a highly distorted fourfold coordination; moreover, the tetrahedral chain configuration is little changed along the series, and the MI polyhedral size increases with Zn substitution in M2. An implication of the present work is the interpretation of the partitioning of Zn between clino-pyroxene and melt. The distribution coefficients of Zn and Co are quite different in rocks of the same composition, despite their very similar ionic radius, and the difference is related to the preference of Zn for the M2 site, where Zn may find a suitable atomic coordination.

${\mathrm{BiMnO}}_{3}$ (BMO), ferromagnetic (FM) below ${T}_{c}\ensuremath{\simeq}100\phantom{\rule{0.28em}{0ex}}\mathrm{K}$, was believed to also be ferroelectric (FE) due to a noncentrosymmetric $C2$ structure, until diffraction data indicated that its space group is the centrosymmetric $C2/c$. Here we present infrared phonon spectra of BMO, taken on a mosaic of single crystals, which are consistent with $C2/c$ at any $Tg10\phantom{\rule{0.28em}{0ex}}\mathrm{K}$, as well as room-temperature Raman data which strongly support this conclusion. We also find that the infrared intensity of several phonons increases steadily for $T\ensuremath{\rightarrow}0$, causing the relative permittivity of BMO to vary from 18.5 at 300 K to 45 at 10 K. At variance with FE materials of the displacive type, no appreciable softening has been found in the infrared phonons. Both their frequencies and intensities, moreover, appear insensitive to the FM transition at ${T}_{c}$.

The influence of thermal treatments on the properties of mixed bromide-iodide organolead perovskites (MAPbI3-xBrx, MA = CH3NH3) is investigated in films prepared in air by single-step solution processes based on different precursor solutions. Initially, the bandgap energy (EG) dependence on composition is reconsidered on films obtained by mixtures of trihalide solutions. An EG(x) relation is obtained that is expected to be independent of the film properties and can be used to assess perovskite composition. In these samples, recombination centers are observed whose energy depth increases with x, likely involving the simultaneous presence of iodide and bromide, while the Urbach energy increases with the grain surface-to-volume ratio, which points out that the defects giving sub-bandgap absorption originate from grain boundaries. Trihalide mixtures allow perovskite synthetic processes suitable for solar cell production, being fast and reproducible. A slight MABr excess in the solution made of MABr and PbI2 gives MAPbI2Br films free of PbI2 phases and with a high compositional stability, but nonradiative recombination channels can make the material not appropriate for high efficiency solar cells. Finally, the solution made of MAI and PbBr2 (3:1 molar ratio) is little promising for solar cell production because its nonstoichiometric nature makes synthesis reproducibility an issue.

The BiMnO3 perovskite is a very interesting multiferroic material that, once synthesized at high pressure and high temperature, survives as a metastable phase at ambient conditions. We investigated ceramic samples prepared in different conditions (temperature, pressure, and composition), and the existence of polymorphism at room temperature was clearly evidenced by electron diffraction and high-resolution electron microscopy in all the samples. A new polymorph, characterized by a different distortion of the perovskite basic cell, was found to coexist as a minor phase with the well-known C2 monoclinic form. The new polymorph, which can be described by a triclinic (pseudorhombohedral) superstructure with a = 13.62 angstrom, b = 13.66 angstrom, c = 13.66 angstrom, alpha = 110.0 degrees, beta = 108.8 degrees, and gamma = 108.8 degrees, is mostly segregated at the grain surface. Magnetic characterizations revealed for this second form a critical temperature of 107 K, a few degrees above the ferromagnetic transition of the monoclinic C2 form measured at 99 K. The new phase disappears by reheating the samples at ambient pressure, suggesting the idea of a higher energy polymorph, which kinetically converts in the usual phase once a sufficient temperature has been achieved.

We report the crystal growth and the structural refinement of NaMn7O12, a manganite having a double perovskite structure. As in many similar compounds, there is coexistence of Mn3+ and Mn4+ but in this material they orderly occupy different sites for crystallographic reasons. Therefore, this peculiar structure can be considered as a model system for studying complex mechanisms such as charge, orbital and spin ordering. High purity bulk samples and “large” single crystals are needed to study tiny modifications in the crystallographic and magnetic structures associated to the ordering phenomena. Almost single phase (more than 96% pure) and single crystals (up to about 150 µm) of NaMn7O12 were synthesized by solid state reaction under pressure in a multi-anvil apparatus. Single crystal x-ray diffraction and SEM analysis have been used to characterize the crystals. The structure refinement indicates that NaMn7O12 crystallizes in the cubic Im3 space group, with a = 7.312 A and Z = 2. Further studies are in progress to optimize the synthesis conditions, in order to grow larger crystals. (© 2005 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim)

Vn-xTixO2n-1 Magneli phases have been synthesized under vacuum in powder form (n = 4, 0 ≤ x ≤ 0.4) and crystals (n = 4 and 5, x = 0.5 and 1.4, respectively), grown by chemical vapour transport in closed ampoules. TeCl4 and NH4Cl were used as transporting agents. Needle-shaped crystals as long as 200-300 micrometers or 2-3 mm were obtained when in presence of NH4Cl or TeCl4, respectively. The powder and crystal structures were examined by X-ray diffraction and the transport and magnetic characteristics were measured.. The powders resulted to be single-phase and the relevant composition was assumed to be equal to the nominal one. The overall stoichiometry of compounds, n, was determined from single crystal X-ray diffraction data. The Ti content, x, was deduced from the elementary cell volume, by applying the Vegard law. Crystals were mainly untwinned and of good quality. The elementary cell of both, powders and crystals, was triclinic (P-1) and did not change with doping. DC electrical resistivity of the crystals was measured in a four-points (van der Pauw) configuration. DC magnetic susceptibility of the powders was measured in a SQUID magnetometer. The Ti doping was found to progressively smooth and finally to suppress the magnetic transitions occurring in the V4O7. The metal-insulator transitions observed in V4O7 and V5O9, at around 235 and 125 K respectively, were not observed in the doped crystals, thus indicating some significant change of the electronic structure of the V oxides. (© 2005 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim)

The importance of pure-phase titanium oxide materials as catalysts, sensors, and photonic band-gap materials has been growing steadily. Recently, more attention has been focused on nanostructured titanium oxide showing controlled and periodic porosity on a nanometric scale. The nanocrystal size control of porous nanostructured titanium oxide in an anatase form is a crucial step for the organic template method. Simple template removal by evaporation in an inert atmosphere is reported in this article and compared with the calcination technique usually reported in the literature. The proposed method allows the formation of a double-porous (macro and meso) anatase phase. We demonstrate that it highly preserves the macropore order into a titanium oxide material and induces narrowly dispersed mesopores by controlling the nano-crystal size that is kept around 6 nm. For the proposed method, polystyrene beads are particularly suitable as templates, being evaporated in the temperature range of anatase existence. The final high surface area makes the materials appealing for applications as photocatalysts or sensors.

Co 80 Pt 20 films of varying thicknesses have been prepared by electrodeposition on Cu seed layers. The films display perpendicular magnetic anisotropy and large coercivities. Soft/hard bilayers were subsequently obtained by sputter deposition of Ni 80 Fe 20 layers. A thorough experimental analysis of the magnetization reversal is carried out in samples with different layer thicknesses by measuring the total susceptibility, the recoil initial susceptibility and the ac reversible susceptibility as a function of the applied field, allowing to discriminate between reversible and irreversible processes and to point out exchange-spring behaviour.

Transition metal fluorides with tetragonal tungsten bronze (TTB) structure, having general formula KxMIIxMIII1-xF3 with 0.4 < x < 0.6 and M belonging to transition metals, have been studied over the past decades because of the frustrated magnetic ordering arising at low temperature. We investigated the structural properties of TTB fluorides by transmission electron microscopy (TEM). The results, coupled with an accurate structure analysis performed by single-crystal XRD on K0.53FeF3, revealed ferroelectricity and a unified structural description of these materials, where charge order and tilt modulations coexist, each one with its own periodicity differently commensurate to the conventional TTB cell. Whereas the charge order is peculiar of the mixed valence fluorides, the nature of the tilt modulation is clearly associable to the structural features of TTB niobates, suggesting also for the fluoride bronzes the existence of a generalized ferroelectric-ferroelastic behavior at room temperature.

AlVO4 is a relatively new sensor material derived from V2O5/Al2O3 mixtures to selectively detect NO and NO2 gases. Previous studies carried out in order to determine its structural, absorptive and sensory properties indicate that the AlVO4 is not the only single phase. This work deals with the synthesis of the compound by the ceramic and the nitrate decomposition methods, and by the sol gel route. The Rietveld refinement of the compound was carried out in order to determine its crystal structure. Single phase of AlVO4 was successfully obtained via the nitrate decomposition and the sol gel methods. Thereafter, films prepared by the sol gel route were deposited on alumina and Si/SiO2/Pt substrates and characterized by SEM and X-ray diffraction. The electric characterization of the AlVO4 on alumina substrate film is also presented.

Results of a colloidal crystal growth by vertical deposition of nanometric polystyrene beads on a glass substrate under oscillatory shear are reported in this paper. This technique of deposition enabled us to study an early stage of the growth of films as a function of the bead concentration in the water suspension. The surprising analogy between single layer growth and the bulk colloidal crystal behavior has been found. Indeed, the sequence of transitions from low density disordered (LDD) phase to intermediate density ordered phase and then to high density ordered phase with increasing bead concentration has been observed. © 2003 Elsevier Science B.V. All rights reserved.

Measurements of magnetization and of resistivity under pressure on Ba 1-x Sr x VS 3 single crystals show that Sr-induced chemical pressure progressively weakens the antiferromagnetic correlations responsible for the metal-insulator transition. The antiferromagnetic ordering temperature, TX = 30 K at x = 0, vanishes at x = 0.08. At larger x, a ferromagnetic order appears with TC = 21.5 K at x = 0.18. The key-parameter favoring the metallic state is found to be the compression of the VS 6 octahedra and we predict a metallic state at 0 K for a V–S distance of 2.33 Å. The stabilization effect of the metallic state provided by the chemical pressure is supported by first principles band structure calculations performed by using the Vienna ab initio simulation package (VASP) within the projector augmented–wave (PAW) method in the local density approximation (LDA) + U scheme.

We have developed a novel method to grow ordered layers of monodisperse colloids on a flat substrate. The evaporation of the colloidal suspension in the presence of the inclined substrate is strengthened by an external gas flux directed on the meniscus. The meniscus oscillations caused by the gas flux have an evident effect on the ordering of the spheres on the substrate. Thick films (more than 150 layers in a single-step deposition) of large area single crystals (∼1 cm 2 ) can be obtained in a very short time (∼1 cm/h maximum growth rate) and from very diluted suspensions (up to 0.022% volume fraction).

[reaction: see text] The radical chain reaction of benzenethiol with alkynylthiol esters provides a new, valuable protocol for the tin-free generation of acyl radicals that arise from intramolecular substitution at sulfur by the initial sulfanylvinyl radicals.

The radical chain reactions of a variety of acyclic and cyclic α-azido ketones with tributyltin hydride have been investigated. The derived N-(tributylstannyl)aminyl radicals normally undergo H-abstraction reaction yielding corresponding amines, and thence symmetrical pyrazines by subsequent self-condensation, in competition with 1,2-H-migration from the α-carbon to nitrogen leading to α-imino ketone decomposition products with loss of the chain-carrying tributyltin radical. The noteworthy occurrence of a quite uncommon radical 1,2-hydrogen-atom shift is considered to be largely due to consequent formation of a highly stable, captodative carbon-centred radical. In contrast with our previous N-stannylaminyl radicals produced from α-azido-β-keto esters, the present aminyl congeners give poor amounts (or even none) of nitrogen-inserted amides/lactams, which are envisaged to arise from intramolecular three-membered cyclisation onto the ketone moiety followed by β-scission of the resultant alkoxyl radical. It is inferred that adequate stabilisation of the eventual ring-opened carbon radical be a major factor for the successful outcome of the regiospecific nitrogen insertion process. Evidence is also presented that chemoselective attack of tris(trimethylsilyl)silyl radical to the ketone oxygen of an α-azido ketone gives rise to deazidation as a likely consequence of β-elimination of azidyl radical by the ensuing α-silyloxyalkyl radical. X-Ray crystal structure analyses of the bromo ketone 5a , the azido ketone 5b , the caprolactam 22 , and the pyrazine 26 have been performed.

The new title compound is prepared by solid state reaction of a stoichiometric mixture of PbO, MnCO3, and WO3 (N2 stream, 800 °C for 2 h and 820 °C for 4 h).

In this paper we describe the new ferri-electric compound Pb2MnWO6 (PMW), a double perovskite that can be considered as a novel structural prototype showing complex nuclear structure and interesting electric properties. According to single-crystal synchrotron data, PMW crystallizes in the noncentrosymmetric polar group Pmc21, in which the two symmetry-independent lead atoms give rise to a ferrielectric arrangement. The accurate crystallographic characterization indicates the presence of a complex distortion of the perovskite lattice driven by the local instability induced by the 6s(2) lone pair of the lead atoms. These peculiar structural features are confirmed by the complete electrical characterization of the system. Dielectric and transport measurements indicate an insulating character of the sample, while pyroelectric measurements point out a ferrielectric state characterized by different contributions. The magnetic transition at 45 K is accompanied by a magnetostrictive effect indicating a probable spin-lattice coupling. The characterizations carried out on PMW, showing the evidence of a coexistence of antiferromagnetism and ferrielectricity at low temperature, could lead to the definition of a new class of multiferroic materials.

The structural behavior of BiMnO3 under pressure was studied in a quantitative way by single-crystal synchrotron Xray diffraction up to 36 GPa. Two phase transitions were observed at moderate pressures (1 and 6 GPa, respectively), leading the system at first to the P2(1)/c and then to the Puma symmetry. The breaking of C-centering in the first transition does not affect significantly Jahn-Teller (JT) distortion and orbital order (OO) but determines a significant change in the cooperative tilting of the MnO6 octahedra. The second transition increases the symmetry to orthorhombic, leading to a Pnma structure similar to the O' structure of LaMnO3, characterized by a > c > b root 2. No symmetry change was observed above 7.1 GPa, but the different compressibility of the lattice parameters (in particular, the b axis) leads at first to a pseudocubic phase (approximate to 30 GPa) and then to different parameter ratios (b/ root 2 > c > a). Even if the JT distortion is continuously reduced with increasing pressure, it is retained, together with the resulting 00, until the highest measured pressure, pointing out the relevant role of the distortion induced by the Bi3+ lone pair in stabilizing the JT distortion.