Structural transitions under high-pressure in a langasite-type multiferroic Ba3TaFe3Si2O14

The iron containing langasite family compound Ba₃Ta⁵⁷Fe₃Si₂O₁₄ was studied at high pressure up to 30 GPa at room temperature by means of in situ X-ray diffraction, Raman and Mössbauer spectroscopies in diamond anvil cell. Two structural transitions at pressures ∼5 and ∼20 GPa are observed. At ∼5 GPa, the low-pressure trigonal P321 phase undergoes phase transition to the most likely P3 structure as manifested by slight increase in the c/a ratio and by anomalies of the Mössbauer and Raman spectra parameters. At ∼20 GPa, the first order phase transition to monoclinic structure occurred with a drop of unit cell volume by 9%. The appearance of the ferroelectric state at such transitions is discussed in connection with the multiferroic properties.     

Characterizing Pressure‐Induced Uranium CH Agostic Bonds

The diuranium(III) compound [UN′′₂]₂(μ‐η⁶:η⁶‐C₆H₆) (N′′=N(SiMe₃)₂) has been studied using variable, high‐pressure single‐crystal X‐ray crystallography, and density functional theory . In this compound, the low‐coordinate metal cations are coupled through π‐ and δ‐symmetric arene overlap and show close metal? CH contacts with the flexible methyl CH groups of the sterically encumbered amido ligands. The metal–metal separation decreases with increasing pressure, but the most significant structural changes are to the close contacts between ligand CH bonds and the U centers. Although the interatomic distances are suggestive of agostic‐type interactions between the U and ligand peripheral CH groups, QTAIM (quantum theory of atoms‐in‐molecules) computational analysis suggests that there is no such interaction at ambient pressure. However, QTAIM and NBO analyses indicate that the interaction becomes agostic at 3.2 GPa.     

Theoretical study of the structural,elastic, electronic and optical properties of XCaF3 (X = K and Rb)

The PLANE WAVE pseudo-potential method within density functional theory (DFT) has been used to investigate the structural, elastic, electronic and optical properties of XCaF₃ (X = K and Rb) insulating. The studied compounds show a weak resistance to shear deformation compared to the resistance to the unidirectional compression. KCaF₃ and RbCaF₃ are considered ductile. The elastic constants and related parameters were predicted. The stiffness is more important in KCaF₃, whereas, the lateral expansion is more important in RbCaF₃. KCaF₃ and RbCaF₃ have R- Г indirect band gap. The main peaks in the imaginary part of the dielectric function correspond to the transition from the occupied state F₋p to the unoccupied states Ca: s or K, Rb: p. At lower energies, KCaF₃ and RbCaF₃ show the same optical properties. Under pressure effect, the peaks of imaginary part of dielectric function were shifted toward high energy.     

Ba3P5N10Br:Eu2+: A Natural‐White‐Light Single Emitter with a Zeolite Structure Type

Illumination sources based on phosphor‐converted light emitting diode (pcLED) technology are nowadays of great relevance. In particular, illumination‐grade pcLEDs are attracting increasing attention. Regarding this, the application of a single warm‐white‐emitting phosphor could be of great advantage. Herein, we report the synthesis of a novel nitridophosphate zeolite Ba₃P₅N₁₀Br:Eu²⁺. Upon excitation by near‐UV light, natural‐white‐light luminescence was detected. The synthesis of Ba₃P₅N₁₀Br:Eu²⁺ was carried out using the multianvil technique. The crystal structure of Ba₃P₅N₁₀Br:Eu²⁺ was solved and refined by single‐crystal X‐ray diffraction analysis and confirmed by Rietveld refinement and FTIR spectroscopy. Furthermore, spectroscopic luminescence measurements were performed. Through the synthesis of Ba₃P₅N₁₀Br:Eu²⁺, we have shown the great potential of nitridophosphate zeolites to serve as high‐performance luminescence materials.     

Rattling in the Quadruple Perovskite CuCu3V4O12

Of particular interest is a peculiar motion of guest atoms or ions confined to nanospace in cage compounds, called rattling. While rattling provides unexplored physical properties through the guest–host interactions, it has only been observed in a very limited class of materials. Herein, we introduce an A‐site‐ordered quadruple perovskite, CuCu₃V₄O₁₂, as a new family of cage compounds. This novel AA′₃B₄O₁₂‐type perovskite has been obtained by a high‐pressure synthesis technique and structurally characterized to have cubic Im$\bar 3$ symmetry with an ionic model of Cu²⁺Cu²⁺₃V⁴⁺₄O₁₂. The thermal displacement parameter of the A‐site Cu²⁺ ion is as large as U_iso≈0.045 Ų at 300 K, indicating its large‐amplitude thermal oscillations in the oversized icosahedral cages. Remarkably, the presence of localized phonon modes associated with rattling of the A‐site Cu²⁺ ion manifests itself in the low‐temperature specific heat data. This work sheds new light on the structure–property relations in perovskites.     

Barium‐Mediated Cross‐Dehydrocoupling of Hydrosilanes with Amines: A Theoretical and Experimental Approach

Alkaline‐earth (most prominently barium) complexes of the type [Ae{N(SiMe₃)₂}₂?(THF)_x] and [{N^N}Ae{N(SiMe₃)₂}?(THF)_x] are very active and productive precatalysts (TON=396, TOF up to 3600 h^?1; Ca相似文献   

Locating Gases in Porous Materials: Cryogenic Loading of Fuel‐Related Gases Into a Sc‐based Metal–Organic Framework under Extreme Pressures

An alternative approach to loading metal organic frameworks with gas molecules at high (kbar) pressures is reported. The technique, which uses liquefied gases as pressure transmitting media within a diamond anvil cell along with a single‐crystal of a porous metal–organic framework, is demonstrated to have considerable advantages over other gas‐loading methods when investigating host–guest interactions. Specifically, loading the metal–organic framework Sc₂BDC₃ with liquefied CO₂ at 2 kbar reveals the presence of three adsorption sites, one previously unreported, and resolves previous inconsistencies between structural data and adsorption isotherms. A further study with supercritical CH₄ at 3–25 kbar demonstrates hyperfilling of the Sc₂BDC₃ and two high‐pressure displacive and reversible phase transitions are induced as the filled MOF adapts to reduce the volume of the system.     

Near‐forward/high‐pressure‐backward Raman study of Zn1 − xBexSe (x ~ 0.5) – evidence for percolation behavior of the long (Zn―Se) bond

The apparently universal 1‐bond → 2‐mode percolation behavior in the Raman spectra of zincblende semiconductor alloys is generally observed for the short bond only, and not for the long one. In this work we perform a combined high‐pressure‐backward/near‐forward Raman study of the leading percolation‐type (Zn,Be)Se alloy (~50 at.% Be), which exhibits a distinct percolation doublet in the spectral range of its short Be―Se bond, in search of a Zn―Se analogue. The high‐pressure‐backward insight is not conclusive per se, but clarifies the perspective behind the near‐forward Raman study. The latter reveals an unique Zn―Se phonon–polariton. Its fair contour modeling depending on the scattering angle is achieved within the linear dielectric approach, based on ellipsometry measurement of the ZnBeSe refractive index. Somewhat surprisingly this reveals that the phonon–polariton in question is a ‘fractional’ one in that it carries only half of the available Zn―Se oscillator strength, as ideally expected in case of a BeSe‐like bimodal Raman behavior of the long Zn―Se bond. Copyright © 2015 John Wiley & Sons, Ltd.     

Understanding guest and pressure‐induced porosity through structural transition in flexible interpenetrated MOF by Raman spectroscopy

Interpenetrating metal organic frameworks are interesting functional materials exhibiting exceptional framework properties. Uptake or exclusion of guest molecules can induce sliding in the framework making it porous or non‐porous. To understand this dynamic nature and how framework interaction changes during sliding, metal organic framework (MOF) 508 {Zn(BDC)( 4,4′‐Bipy)_0.5 · DMF(H₂O)_0.5} was selected for study. We have investigated structural transformation in MOF‐508 under variable conditions of temperature, pressure and gas loading using Raman spectroscopy and substantiated it with IR studies and density functional theory (DFT) calculations. Conformational changes in the organic linkers leading to the sliding of the framework result in changes in Raman spectra. These changes in the organic linkers are measured as a function of high pressure and low temperature, suggesting that the dynamism in MOF‐508 framework is driven by ligand conformation change and inter‐linker interactions. The presence of Raman signatures of adsorbed CO₂ and its librational mode at 149 cm⁻¹ suggests cooperative adsorption of CO₂ in the MOF‐508 framework, which is also confirmed from DFT calculations that give a binding energy of 34 kJ/mol. Copyright © 2015 John Wiley & Sons, Ltd.     

High P–T Raman study of transitions in relaxor multiferroic Pb(Fe0.5Nb0.5)O3

The vibrational and structural properties of Pb(Fe_0.5Nb_0.5)O₃ have been investigated using Raman spectroscopy up to 40 GPa at 300 K and from 300 to 415 K at selected pressures. The measurements reveal three phase transitions, at 5.5, 8.7, and 24 GPa at room temperature. The temperature dependences of the spectra indicate transitions at 1.5 GPa, at 335 and 365 K. The results are consistent with the appearance of an intermediate tetragonal P4mm phase between the ferroelectric R3m and paraelectric Pm‐3m phases. A P–T phase diagram is proposed that allows further insight into the magnetoelectric coupling present in this material. Copyright © 2015 John Wiley & Sons, Ltd.