Stabilization of N6 and N8 anionic units and 2D polynitrogen layers in high-pressure scandium polynitrides.

Nitrogen catenation under high pressure leads to the formation of polynitrogen compounds with potentially unique properties. The exploration of the entire spectrum of poly- and oligo-nitrogen moieties is still in its earliest stages. Here, we report on four novel scandium nitrides, Sc2N6, Sc2N8, ScN5, and Sc4N3, synthesized by direct reaction between yttrium and nitrogen at 78-125 GPa and 2500 K in laser-heated diamond anvil cells. High-pressure synchrotron single-crystal X-ray diffraction reveals that in the crystal structures of the nitrogen-rich Sc2N6, Sc2N8, and ScN5 phases nitrogen is catenated forming previously unknown N66- and N86- units and ∞ 2 ( N 5 3 - ) anionic corrugated 2D-polynitrogen layers consisting of fused N12 rings. Density functional theory calculations, confirming the dynamical stability of the synthesized compounds, show that Sc2N6 and Sc2N8 possess an anion-driven metallicity, while ScN5 is an indirect semiconductor. Sc2N6, Sc2N8, and ScN5 solids are promising high-energy-density materials with calculated volumetric energy density, detonation velocity, and detonation pressure higher than those of TNT.

Stabilization Of The CN3 5- Anion In Recoverable High-pressure Ln3 O2 (CN3 ) (Ln=La, Eu, Gd, Tb, Ho, Yb) Oxoguanidinates.

A series of isostructural Ln3 O2 (CN3 ) (Ln=La, Eu, Gd, Tb, Ho, Yb) oxoguanidinates was synthesized under high-pressure (25-54 GPa) high-temperature (2000-3000 K) conditions in laser-heated diamond anvil cells. The crystal structure of this novel class of compounds was determined via synchrotron single-crystal X-ray diffraction (SCXRD) as well as corroborated by X-ray absorption near edge structure (XANES) measurements and density functional theory (DFT) calculations. The Ln3 O2 (CN3 ) solids are composed of the hitherto unknown CN3 5- guanidinate anion-deprotonated guanidine. Changes in unit cell volumes and compressibility of Ln3 O2 (CN3 ) (Ln=La, Eu, Gd, Tb, Ho, Yb) compounds are found to be dictated by the lanthanide contraction phenomenon. Decompression experiments show that Ln3 O2 (CN3 ) compounds are recoverable to ambient conditions. The stabilization of the CN3 5- guanidinate anion at ambient conditions provides new opportunities in inorganic and organic synthetic chemistry.

On the identification of hyperhydrated sodium chloride hydrates, stable at icy moon conditions.

Sodium chloride is expected to be found on many of the surfaces of icy moons like Europa and Ganymede. However, spectral identification remains elusive as the known NaCl-bearing phases cannot match current observations, which require higher number of water of hydration. Working at relevant conditions for icy worlds, we report the characterization of three "hyperhydrated" sodium chloride (SC) hydrates, and refined two crystal structures [2NaCl·17H2O (SC8.5); NaCl·13H2O (SC13)]. We found that the dissociation of Na+ and Cl- ions within these crystal lattices allows for the high incorporation of water molecules and thus explain their hyperhydration. This finding suggests that a great diversity of hyperhydrated crystalline phases of common salts might be found at similar conditions. Thermodynamic constraints indicate that SC8.5 is stable at room pressure below 235 K, and it could be the most abundant NaCl hydrate on icy moon surfaces like Europa, Titan, Ganymede, Callisto, Enceladus, or Ceres. The finding of these hyperhydrated structures represents a major update to the H2O-NaCl phase diagram. These hyperhydrated structures provide an explanation for the mismatch between the remote observations of the surface of Europa and Ganymede and previously available data on NaCl solids. It also underlines the urgent need for mineralogical exploration and spectral data on hyperhydrates at relevant conditions to help future icy world exploration by space missions.

Tracking structural phase transitions via single crystal x-ray diffraction at extreme conditions: advantages of extremely brilliant source.

Highly brilliant synchrotron source is indispensable to track pressure-induced phenomena in confined crystalline samples in megabar range. In this article, a number of experimental variables affecting the quality high-pressure single-crystal x-ray diffraction data is discussed. An overview of the recent advancements in x-ray diffraction techniques at extreme conditions, in the frame of European Synchrotron Radiation Facility (ESRF)- Extremely Bright Source (EBS), is presented. Particularly, ID15b and ID27 beamlines have profited from the source upgrade, allowing for measurements of a few-micron crystals in megabar range. In case of ID27, a whole new beamline has been devised, including installation of double-multilayer mirrors and double crystal monochromator and construction of custom-made experimental stations. Two case studies from ID27 and ID15b are presented. Hypervalent CsI3crystals, studied up to 24 GPa, have shown a series of phase transitions:Pnma → P-3c1→ Pm-3n. First transition leads to formation of orthogonal linear iodine chains made of I3-. Transformation to the cubic phase at around 21.7 GPa leads to equalization of interatomic I-I distances and formation of homoleptic Inm-chains. The second study investigates elastic properties and structure of jadarite, which undergoes isosymmetric phase transition around 16.6 GPa. Despite a few-micron crystal size, twinning and dramatic loss of crystal quality, associated with pressure-induced phase transitions, crystal structures of both compounds have been determined in a straightforward matter, thanks to the recent developments within ESRF-EBS.

Plastic bending in a semiconducting coordination polymer crystal enabled by delamination.

Coordination polymers (CPs) are a class of crystalline solids that are considered brittle, due to the dominance of directional coordination bonding, which limits their utility in flexible electronics and wearable devices. Hence, engineering plasticity into functional CPs is of great importance. Here, we report plastic bending of a semiconducting CP crystal, Cu-Trz (Trz = 1,2,3-triazolate), that originates from delamination facilitated by the discrete bonding interactions along different crystallographic directions in the lattice. The coexistence of strong coordination bonds and weak supramolecular interactions, together with the unique molecular packing, are the structural features that enable the mechanical flexibility and anisotropic response. The spatially resolved analysis of short-range molecular forces reveals that the strong coordination bonds, and the adaptive C-H···π and Cu···Cu interactions, synergistically lead to the delamination of the local structures and consequently the associated mechanical bending. The proposed delamination mechanism offers a versatile tool for designing the plasticity of CPs and other molecular crystals.

Host-Guest Hydrogen Bonding in High-Pressure Acetone Clathrate Hydrates: In Situ Single-Crystal X-ray Diffraction Study.

The phenomenon of host-guest hydrogen bonding in clathrate hydrate crystal structures and its effect on physical and chemical properties have become subjects of extensive research. Hydrogen bonding has been studied for cubic (sI and sII) and hexagonal (sH) binary clathrates, while it has not been addressed for clathrate structures that exist at elevated pressures. Here, four acetone hydrate clathrates have been grown at high-pressure and low-temperature conditions. In situ single-crystal X-ray diffraction revealed that the synthesized phases possess already known trigonal (sTr), orthorhombic (sO), and tetragonal (sT) crystal structures as well as a previously unknown orthorhombic structure, so-called sO-II. Only sO and sII have previously been reported for acetone clathrates. Structural analysis suggests that acetone oxygens are hydrogen-bonded to the closest water oxygens of the host frameworks. Our discoveries show that clathrate hydrates hosting polar molecules are not as exotic as previously thought and could be stabilized at high-pressure conditions through hydrogen bonding.

Anomalous Volume Changes in the Siliceous Zeolite Theta-1 TON due to Hydrogen Insertion under High-Pressure, High-Temperature Conditions.

High-pressure X-ray diffraction and Raman spectroscopy in a diamond anvil cell were used to study the insertion of the chemical hydrogen storage material, ammonia borane, in the one-dimensional pores of the zeolite theta-1 TON. Heating of this material up to 300 °C under pressures up to 5 GPa resulted in the release of a significant amount of hydrogen due to the conversion of ammonia borane confined in the channels of TON and outside the zeolite to polyaminoborane and then polyiminoborane chains. The filling of TON with hydrogen resulted in a much greater increase in unit cell volume than that corresponding to thermal expansion of normal compact inorganic solids. This process at high temperature is accompanied by a phase transition from the collapsed high-pressure Pbn21 form to the more symmetric Cmc21 phase with expanded pores. This material has a high capacity for hydrogen adsorption under high-temperature, high-pressure conditions.

Tetrahedrally Coordinated sp3-Hybridized Carbon in Sr2CO4 Orthocarbonate at Ambient Conditions.

We have synthesized the orthocarbonate Sr2CO4, in which carbon is tetrahedrally coordinated by four oxygen atoms, at moderately high pressures [20(1) GPa] and high temperatures (≈3500 K) in a diamond anvil cell by reacting a SrCO3 single crystal with SrO powder. We show by synchrotron powder X-ray diffraction, Raman spectroscopy, and density functional thoery calculations that this phase, and hence sp3-hybridized carbon in a CO44- group, can be recovered at ambient conditions. The C-O bond distances are all of similar lengths [≈1.41(1) Å], and the O-C-O angles deviate from the ideal tetrahedral angle by a few degrees only.