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.

Probing the Influence of Defects, Hydration, and Composition on Prussian Blue Analogues with Pressure.

The vast compositional space of Prussian blue analogues (PBAs), formula AxM[M'(CN)6]y·nH2O, allows for a diverse range of functionality. Yet, the interplay between composition and physical properties-e.g., flexibility and propensity for phase transitions-is still largely unknown, despite its fundamental and industrial relevance. Here we use variable-pressure X-ray and neutron diffraction to explore how key structural features, i.e., defects, hydration, and composition, influence the compressibility and phase behavior of PBAs. Defects enhance the flexibility, manifesting as a remarkably low bulk modulus (B0 ≈ 6 GPa) for defective PBAs. Interstitial water increases B0 and enables a pressure-induced phase transition in defective systems. Conversely, hydration does not alter the compressibility of stoichiometric MnPt(CN)6, but changes the high-pressure phase transitions, suggesting an interplay between low-energy distortions. AMnCo(CN)6 (AI = Rb, Cs) transition from F4̅3m to P4̅n2 upon compression due to octahedral tilting, and the critical pressure can be tuned by the A-site cation. At 1 GPa, the symmetry of Rb0.87Mn[Co(CN)6]0.91 is further lowered to the polar space group Pn by an improper ferroelectric mechanism. These fundamental insights aim to facilitate the rational design of PBAs for applications within a wide range of fields.

Crystal Structure and Non-Hydrostatic Stress-Induced Phase Transition of Urotropine Under High Pressure.

High-pressure behavior of hexamethylenetetramine (urotropine) was studied in situ using angle-dispersive single-crystal synchrotron X-ray diffraction (XRD) and Fourier-transform infrared absorption (FTIR) spectroscopy. Experiments were conducted in various pressure-transmitting media to study the effect of deviatoric stress on phase transformations. Up to 4 GPa significant damping of molecular librations and atomic thermal motion was observed. A first-order phase transition to a tetragonal structure was observed with an onset at approximately 12.5 GPa and characterized by sluggish kinetics and considerable hysteresis upon decompression. However, it occurs only in non-hydrostatic conditions, induced by deviatoric or uniaxial stress in the sample. This behavior finds analogies in similar cubic crystals built of highly symmetric cage-like molecules and may be considered a common feature of such systems. DFT computations were performed to model urotropine equation of state and pressure dependence of vibrational modes. The first successful Hirshfeld atom refinements carried out for high-pressure diffraction data are reported. The refinements yielded more realistic C-H bond lengths than the independent atom model even though the high-pressure diffraction data are incomplete.

Pressure-Induced Polymerization of Polycyclic Arene-Perfluoroarene Cocrystals: Single Crystal X-ray Diffraction Studies, Reaction Kinetics, and Design of Columnar Hydrofluorocarbons.

Pressure-induced polymerization of aromatic compounds leads to novel materials containing sp3 carbon-bonded networks. The choice of the molecular species and the control of their arrangement in the crystal structures via intermolecular interactions, such as the arene-perfluoroarene interaction, can enable the design of target polymers. We have investigated the crystal structure compression and pressure-induced polymerization reaction kinetics of two polycyclic 1:1 arene-perfluoroarene cocrystals, naphthalene/octafluoronaphthalene (NOFN) and anthracene/octafluoronaphthalene (AOFN), up to 25 and 30 GPa, respectively, using single-crystal synchrotron X-ray diffraction, infrared spectroscopy, and theoretical computations based on density-functional theory. Our study shows the remarkable pressure stability of the parallel arene-perfluoroarene π-stacking arrangement and a reduction of the interplanar π-stacking separations by ca. 19-22% before the critical reaction distance is reached. A further strong, discontinuous, and irreversible reduction along the stacking direction at 20 GPa in NOFN (18.8%) and 25 GPa in AOFN (8.7%) indicates the pressure-induced breakdown of π-stacking by formation of σ-bonded polymers. The association of the structural distortion with the occurrence of a chemical reaction is confirmed by a high-pressure kinetic study using infrared spectroscopy, indicating one-dimensional polymer growth. Structural predictions for the fully polymerized high-pressure phases consisting of highly ordered rods of hydrofluorocarbons are presented based on theoretical computations, which are in excellent agreement with the experimentally determined unit-cell parameters. We show that the polymerization takes place along the arene-perfluoroarene π-stacking direction and that the lateral extension of the columns depends on the extension of the arene and perfluoroarene molecules.

Packing Rearrangements in 4-Hydroxycyanobenzene Under Pressure.

4-hydroxycyanobenzene (4HCB) is a dipolar molecule formed of an aromatic substituted benzene ring with the CN and OH functional groups at the 1 and 4 positions. In the crystalline state, it forms spiral chains via hydrogen bonding, which pack together through π - π interactions. The direct stacking of benzene rings down the a- and b-axes and its π - π interactions throughout the structure gives rise to its semiconductor properties. Here, high-pressure studies are conducted on 4HCB in order to investigate how the packing and intermolecular interactions, related to its semiconductor properties, are affected. High-pressure single-crystal X-ray diffraction was performed with helium and neon as the pressure-transmitting mediums up to 26 and 15 GPa, respectively. The pressure-dependent behaviour of 4HCB in He was dominated by the insertion of He into the structure after 2.4 GPa, giving rise to two phase transitions, and alterations in the π - π interactions above 4 GPa. 4HCB compressed in Ne displayed two phase transitions associated with changes in the orientation of the 4HCB molecules, giving rise to twice as many face-to-face packing of the benzene rings down the b-axis, which could allow for greater charge mobility. In the He loading, the hydrogen bonding interactions steadily decrease without any large deviations, while in the Ne loading, the change in 4HCB orientation causes an increase in the hydrogen bonding interaction distance. Our study highlights how the molecular packing and π - π interactions evolve with pressure as well as with He insertion.

Intrinsic Flexibility of the EMT Zeolite Framework under Pressure.

The roles of organic additives in the assembly and crystallisation of zeolites are still not fully understood. This is important when attempting to prepare novel frameworks to produce new zeolites. We consider 18-crown-6 ether (18C6) as an additive, which has previously been shown to differentiate between the zeolite EMC-2 (EMT) and faujasite (FAU) frameworks. However, it is unclear whether this distinction is dictated by influences on the metastable free-energy landscape or geometric templating. Using high-pressure synchrotron X-ray diffraction, we have observed that the presence of 18C6 does not impact the EMT framework flexibility-agreeing with our previous geometric simulations and suggesting that 18C6 does not behave as a geometric template. This was further studied by computational modelling using solid-state density-functional theory and lattice dynamics calculations. It is shown that the lattice energy of FAU is lower than EMT, but is strongly impacted by the presence of solvent/guest molecules in the framework. Furthermore, the EMT topology possesses a greater vibrational entropy and is stabilised by free energy at a finite temperature. Overall, these findings demonstrate that the role of the 18C6 additive is to influence the free energy of crystallisation to assemble the EMT framework as opposed to FAU.

Complete Set of Elastic Moduli of a Spin-Crossover Solid: Spin-State Dependence and Mechanical Actuation.

Molecular spin crossover complexes are promising candidates for mechanical actuation purposes. The relationships between their crystal structure and mechanical properties remain, however, not well understood. In this study, combining high pressure synchrotron X-ray diffraction, nuclear inelastic scattering, and micromechanical measurements, we assessed the effective macroscopic bulk modulus ( B = 11.5 ± 1.5 GPa), Young's modulus ( Y = 10.9 ± 1.0 GPa), and Poisson's ratio (ν = 0.34 ± 0.04) of the spin crossover complex [FeII(HB(tz)3)2] (tz = 1,2,4-triazol-1-yl). Crystal structure analysis revealed a pronounced anisotropy of the lattice compressibility, which was correlated with the difference in spacing between the molecules as well as by the distribution of the stiffest C-H···N interactions in different crystallographic directions. Switching the molecules from the low spin to the high spin state leads to a remarkable drop of the Young's modulus to 7.1 ± 0.5 GPa both in bulk and thin film samples. The results highlight the application potential of these films in terms of strain (ε = -0.17 ± 0.05%), recoverable stress (σ = -21 ± 1 MPa), and work density ( W/V = 15 ± 6 mJ/cm3).

Pressure dependence of spin canting in ammonium metal formate antiferromagnets.

High-pressure single-crystal X-ray diffraction at ambient temperature and high-pressure SQUID measurements down to 2 K were performed up to ∼2.5 GPa on ammonium metal formates, [NH4][M(HCOO)3] where M = Mn2+, Fe2+, and Ni2+, in order to correlate structural variations to magnetic behaviour. Similar structural distortions and phase transitions were observed for all compounds, although the transition pressures varied with the size of the metal cation. The antiferromagnetic ordering in [NH4][M(HCOO)3] compounds was maintained as a function of pressure, and the magnetic ordering transition temperature changed within a few kelvins depending on the structural distortion and the metal cation involved. These compounds, in particular [NH4][Fe(HCOO)3], showed greatest sensitivity to the degree of spin canting upon compression, clearly visible from the twenty-fold increase in the low-temperature magnetisation for [NH4][Fe(HCOO)3] at 1.4 GPa, and the change from purely antiferromagnetic to weakly ferromagnetic ordering in [NH4][Mn(HCOO)3] at 1 GPa. The variation in the exchange couplings and spin canting was checked with density-functional calculations that reproduce well the increase in canted moment within [NH4][Fe(HCOO)3] upon compression, and suggest that the Dzyaloshinskii-Moriya (DM) interaction is evolving as a function of pressure. The pressure dependence of spin canting is found to be highly dependent on the metal cation, as magnetisation magnitudes did not change significantly for when M = Ni2+ or Mn2+. These results demonstrate that the overall magnetic behaviour of each phase upon compression was not only dependent on the structural distortions but also on the electronic configuration of the metal cation.

SiO_{2} Glass Density to Lower-Mantle Pressures.

The convection or settling of matter in the deep Earth's interior is mostly constrained by density variations between the different reservoirs. Knowledge of the density contrast between solid and molten silicates is thus of prime importance to understand and model the dynamic behavior of the past and present Earth. SiO_{2} is the main constituent of Earth's mantle and is the reference model system for the behavior of silicate melts at high pressure. Here, we apply our recently developed x-ray absorption technique to the density of SiO_{2} glass up to 110 GPa, doubling the pressure range for such measurements. Our density data validate recent molecular dynamics simulations and are in good agreement with previous experimental studies conducted at lower pressure. Silica glass rapidly densifies up to 40 GPa, but the density trend then flattens to become asymptotic to the density of SiO_{2} minerals above 60 GPa. The density data present two discontinuities at ∼17 and ∼60 GPa that can be related to a silicon coordination increase from 4 to a mixed 5/6 coordination and from 5/6 to sixfold, respectively. SiO_{2} glass becomes denser than MgSiO_{3} glass at ∼40 GPa, and its density becomes identical to that of MgSiO_{3} glass above 80 GPa. Our results on SiO_{2} glass may suggest that a variation of SiO_{2} content in a basaltic or pyrolitic melt with pressure has at most a minor effect on the final melt density, and iron partitioning between the melts and residual solids is the predominant factor that controls melt buoyancy in the lowermost mantle.

Control of Multipolar and Orbital Order in Perovskite-like [C(NH2)3]CuxCd1-x(HCOO)3 Metal-Organic Frameworks.

We study the compositional dependence of molecular orientation (multipolar) and orbital (quadrupolar) order in the perovskite-like metal-organic frameworks [C(NH2)3]CuxCd1-x(HCOO)3. Upon increasing the fraction x of Jahn-Teller-active Cu(2+), we observe an orbital disorder/order transition and a multipolar reorientation transition, each occurring at distinct critical compositions xo = 0.45(5) and xm = 0.55(5). We attribute these transitions to a combination of size, charge distribution, and percolation effects. Our results establish the accessibility in formate perovskites of novel structural degrees of freedom beyond the familiar dipolar terms responsible for (anti)ferroelectric order. We discuss the implications of cooperative quadrupolar and multipolar states for the design of relaxor-like hybrid perovskites.

Neon-Bearing Ammonium Metal Formates: Formation and Behaviour under Pressure.

The incorporation of noble gas atoms, in particular neon, into the pores of network structures is very challenging due to the weak interactions they experience with the network solid. Using high-pressure single-crystal X-ray diffraction, we demonstrate that neon atoms enter into the extended network of ammonium metal formates, thus forming compounds Nex [NH4 ][M(HCOO)3 ]. This phenomenon modifies the compressional and structural behaviours of the ammonium metal formates under pressure. The neon atoms can be clearly localised within the centre of [M(HCOO)3 ]5 cages and the total saturation of this site is achieved after ∼1.5 GPa. We find that by using argon as the pressure-transmitting medium, the inclusion inside [NH4 ][M(HCOO)3 ] is inhibited due to the larger size of the argon. This study illustrates the size selectivity of [NH4 ][M(HCOO)3 ] compounds between neon and argon insertion under pressure, and the effect of inclusion on the high-pressure behaviour of neon-bearing ammonium metal formates.

Retraction: Carbon content drives high temperature superconductivity in a carbonaceous sulfur hydride below 100 GPa.

Retraction of 'Carbon content drives high temperature superconductivity in a carbonaceous sulfur hydride below 100 GPa' by G. Alexander Smith et al., Chem. Commun., 2022, 58, 9064-9067, https://doi.org/10.1039/D2CC03170A.

Homologous critical behavior in the molecular frameworks Zn(CN)2 and Cd(imidazolate)2.

Using a combination of single-crystal and powder X-ray diffraction measurements, we study temperature- and pressure-driven structural distortions in zinc(II) cyanide (Zn(CN)2) and cadmium(II) imidazolate (Cd(im)2), two molecular frameworks with the anticuprite topology. Under a hydrostatic pressure of 1.52 GPa, Zn(CN)2 undergoes a first-order displacive phase transition to an orthorhombic phase, with the corresponding atomic displacements characterized by correlated collective tilts of pairs of Zn-centered tetrahedra. This displacement pattern sheds light on the mechanism of negative thermal expansion in ambient-pressure Zn(CN)2. We find that the fundamental mechanical response exhibited by Zn(CN)2 is mirrored in the temperature-dependent behavior of Cd(im)2. Our results suggest that the thermodynamics of molecular frameworks may be governed by considerations of packing efficiency while also depending on dynamic instabilities of the underlying framework topology.

Effect of synchrotron X-ray radiation damage on phase transitions in coordination polymers at high pressure.

The high-pressure phase-transition behaviour of metal-organic frameworks and coordination polymers upon varying degrees of X-ray irradiation are highlighted with four example studies. These show that, in certain cases, the radiation damage, while not extreme in changing unit-cell values, can impact the existence of a phase transition. In particular, pressure-induced phase transitions are suppressed after a certain absorbed dose threshold is reached for the sample. This is thought to be due to partial amorphization and/or defect formation in the sample, hindering the co-operative structural distortions needed for a phase transition. The high-pressure experiments were conducted with several crystals within the sample chamber in order to measure crystals with minimal X-ray irradiation at the highest pressures, which are compared with the crystals measured continuously upon pressure increase. Ways to minimize radiation damage are also discussed within the frame of high-pressure experiments.

Understanding multiscale structure-property correlations in PVDF-HFP electrospun fiber membranes by SAXS and WAXS.

Electrospinning is a versatile technique to produce nanofibrous membranes with applications in filtration, biosensing, biomedical and tissue engineering. The structural and therefore physical properties of electrospun fibers can be finely tuned by changing the electrospinning parameters. The large parameter window makes it challenging to optimize the properties of fibers for a specific application. Therefore, a fundamental understanding of the multiscale structure of fibers and its correlation with their macroscopic behaviors is required for the design and production of systems with dedicated applications. In this study, we demonstrate that the properties of poly(vinylidene fluoride-co-hexafluoro propylene) (PVDF-HFP) electrospun fibers can be tuned by changing the rotating drum speed used as a collector during electrospinning. Indeed, with the help of multiscale characterization techniques such as scanning electron microscopy (SEM), small-angle X-ray scattering (SAXS), and wide-angle X-ray scattering (WAXS), we observe that increasing the rotating drum speed not only aligns the fibers but also induces polymeric chain rearrangements at the molecular scale. Such changes result in enhanced mechanical properties and an increase of the piezoelectric ß-phase of the PVDF-HFP fiber membranes. We detect nanostructural deformation behaviors when the aligned fibrous membrane is uniaxially stretched along the fiber alignment direction, while an increase in the alignment of the fibers is observed for randomly aligned samples. This was analyzed by performing in situ SAXS measurements coupled with uniaxial tensile loading of the fibrous membranes along the fiber alignment direction. The present study shows that fibrous membranes can be produced with varying degrees of fiber orientation, piezoelectric ß-phase content, and mechanical properties by controlling the speed of the rotating drum collector during the fiber production. Such aligned fiber membranes have potential applications for neural or musculoskeletal tissue engineering.

Carbon content drives high temperature superconductivity in a carbonaceous sulfur hydride below 100 GPa.

We report a previously unobserved superconducting state of the photosynthesized carbonaceous sulfur hydride (C-S-H) system with a maximum TC of 191(1) K below 100 GPa. The properties of C-S-H are dependent on carbon content, and X-ray diffraction and simulations reveal the system remains molecular-like up to 100 GPa.

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.

Enhancing the chemical flexibility of hybrid perovskites by introducing divalent ligands.

Herein we report the synthesis and structures of [(CH3)2NH2]Er(HCO2)2(C2O4) and [(NH2)3C]Er(HCO2)2(C2O4), in which the inclusion of divalent oxalate ligands allows for the exclusive incorporation of A+ and B3+ cations in an ABX3 hybrid perovskite structure for the first time. We rationalise the observed thermal expansion of these materials, including negative thermal expansion, and find evidence for weak antiferromagnetic coupling in [(CH3)2NH2]Er(HCO2)2(C2O4).

Effect of Alkali and Trivalent Metal Ions on the High-Pressure Phase Transition of [C2H5NH3]MI 0.5MIII 0.5(HCOO)3 (MI = Na, K and MIII = Cr, Al) Heterometallic Perovskites.

We report the high-pressure behavior of two perovskite-like metal formate frameworks with the ethylammonium cation (EtAKCr and EtANaAl) and compare them to previously reported data for EtANaCr. High-pressure single-crystal X-ray diffraction and Raman data for EtAKCr show the occurrence of two high-pressure phase transitions observed at 0.75(16) and 2.4(2) GPa. The first phase transition involves strong compression and distortion of the KO6 subnetwork followed by rearrangement of the -CH2CH3 groups from the ethylammonium cations, while the second involves octahedral tilting to further reduce pore volume, accompanied by further configurational changes of the alkyl chains. Both transitions retain the ambient P21/n symmetry. We also correlate and discuss the influence of structural properties (distortion parameters, bulk modulus, tolerance factors, and compressibility) and parameters calculated by using density functional theory (vibrational entropy, site-projected phonon density of states, and hydrogen bonding energy) on the occurrence and properties of structural phase transitions observed in this class of metal formates.

Spin crossover in the Prussian blue analogue FePt(CN)6 induced by pressure or X-ray irradiation.

The spin state of the Prussian blue analogue FeIIPtIV(CN)6 is investigated in response to temperature, pressure, and X-ray irradiation. While cooling to 10 K maintains the high-spin state of FeII, compression at ambient temperature induces a first-order spin-crossover (SCO) transition with a small hysteresis loop (p↑ = 0.8 GPa, p↓ = 0.6 GPa). In addition, the high-spin to low-spin transition can be initiated at lower pressure through increased X-ray irradiation. Our study highlights a cooperative SCO with moderate pressure in a porous Prussian blue analogue.