Fe4(OAc)10[EMIM]2: Novel Iron-Based Acetate EMIM Ionic Compound.

We synthesized and characterized a novel iron(II) aceto EMIM coordination compound, which has a simplified empirical formula Fe4(OAc)10[EMIM]2, in two different hydration forms: as anhydrous monoclinic compound and triclinic dihydrate Fe4(OAc)10[EMIM]2·2H2O. The dihydrate compound is isostructural with recently reported Mn4(OAc)10[EMIM]2·2H2O, while the anhydrate is a superstructure of the Mn counterpart, suggesting the existence of solid solutions. Both new Fe compounds contain chains of Fe2+ octahedrally coordinated exclusively by acetate groups. The EMIM moieties do not interact directly with the Fe2+ and contribute to the structural framework of the compound through van der Waals forces and C-H···O hydrogen bonds with the acetate anions. The compounds have a melting temperature of ∼94 °C; therefore, they can be considered metal-containing ionic liquids. Differential thermal analysis indicates three endothermic transitions associated with melting, structural rearrangement in the molten state at about 157 °C, and finally, thermal decomposition of the Fe4(OAc)10[EMIM]2. Thermogravimetric analyses indicate an ∼72 wt % mass loss during the decomposition at 280-325 °C. The Fe4(OAc)10[EMIM]2 compounds have higher thermal stability than their Mn counterparts and [EMIM][OAc] but lower compared to iron(II) acetate. Temperature-programmed desorption coupled with mass spectrometry shows that the decomposition pathway of the Fe4(OAc)10[EMIM]2 involves four distinct regimes with peak temperatures at 88, 200, 267, and 345 °C. The main species observed in the decomposition of the compound are CH3, H2O, N2, CO, OC-CH3, OH-CO, H3C-CO-CH3, and H3C-O-CO-CH3. Variable-temperature infrared vibrational spectroscopy indicates that the phase transition at 160-180 °C is associated with a reorientation of the acetate ions, which may lead to a lower interaction with the [EMIM]+ before the decomposition of the Fe4(OAc)10[EMIM]2 upon further heating. The Fe4(OAc)10[EMIM]2 compounds are porous, plausibly capable of accommodating other types of molecules.

The influence of δ-(Al,Fe)OOH on seismic heterogeneities in Earth's lower mantle.

The high-pressure phases of oxyhydroxides (δ-AlOOH, ε-FeOOH, and their solid solution), candidate components of subducted slabs, have wide stability fields, thus potentially influencing volatile circulation and dynamics in the Earth's lower mantle. Here, we report the elastic wave velocities of δ-(Al,Fe)OOH (Fe/(Al + Fe) = 0.13, δ-Fe13) to 79 GPa, determined by nuclear resonant inelastic X-ray scattering. At pressures below 20 GPa, a softening of the phonon spectra is observed. With increasing pressure up to the Fe3+ spin crossover (~ 45 GPa), the Debye sound velocity (vD) increases. At higher pressures, the low spin δ-Fe13 is characterized by a pressure-invariant vD. Using the equation of state for the same sample, the shear-, compressional-, and bulk-velocities (vS, vP, and vΦ) are calculated and extrapolated to deep mantle conditions. The obtained velocity data show that δ-(Al,Fe)OOH may cause low-vΦ and low-vP anomalies in the shallow lower mantle. At deeper depths, we find that this hydrous phase reproduces the anti-correlation between vS and vΦ reported for the large low seismic velocity provinces, thus serving as a potential seismic signature of hydrous circulation in the lower mantle.

Synthesis, Characterization, and Crystal Structures of Two New Manganese Aceto EMIM Ionic Compounds with Chains of Mn2+ Ions Coordinated Exclusively by Acetate.

We synthesized and determined crystal structures of two manganese(II) aceto EMIM coordination compounds with simplified empirical formulas Mn4(OAc)10[EMIM]2 and Mn4(OAc)10[EMIM]2·2H2O. Both compounds feature extended chains of Mn2+ octahedrally coordinated exclusively by acetate anions, which has been observed for the first time. The EMIM moieties and water molecules participate in hydrogen bonding with acetate anions but do not directly interact with the metal cation. Both compounds have melting temperatures around 120 °C and can be considered as (non-room-temperature) ionic liquids. The structural arrangement represented by the two title compounds is robust in terms of accommodating other types of cations and allows for tuning of physical properties of the ionic liquid by means of cation substitution. Thermal analysis results obtained using TGA-DSC and VT IR suggest melting phase transitions around 120 °C, followed by structural rearrangement in the molten state taking place around 140-160 °C. Compounds I and II have a higher thermal stability range compared to [EMIM][OAc] ionic liquid, with an onset decomposition temperature above 260 °C.

Pressure-Induced Large Volume Collapse, Plane-to-Chain, Insulator to Metal Transition in CaMn2Bi2.

In situ high pressure single crystal X-ray diffraction study reveals that the quantum material CaMn2Bi2 undergoes a unique plane to chain structural transition between 2 and 3 GPa, accompanied by a large volume collapse. Puckered Mn-Mn honeycomb layer converts to quasi-one-dimensional (1D) zigzag chains above the phase transition pressure. Single crystal measurements reveal that the pressure-induced structural transformation is accompanied by a dramatic 2 orders of magnitude drop of resistivity. Although the ambient pressure phase displays semiconducting behavior at low temperatures, metallic temperature dependent resistivity is observed for the high pressure phase, as surprisingly, are two resistivity anomalies with opposite pressure dependences, while one of them could be a magnetic transition and the other originates from Fermi surface instability. Assessment of the total energies for hypothetical magnetic structures for high pressure CaMn2Bi2 indicates that ferrimagnetism is thermodynamically favored.

Enhanced Néel temperature in EuSnP under pressure.

We present the combined results of single crystal X-ray diffraction, physical properties characterization, and theoretical assessment of EuSnP under high pressure. Single crystals of EuSnP prepared using Sn self-flux crystallize in the tetragonal NbCrN-type crystal structure (S.G. P4/nmm) at ambient pressure. Previous studies have shown that for Eu ions, seven unpaired electrons impart a 2+ oxidation state. Assuming the oxidation states of Eu to be +2 and P to be -3, each Sn will donate one electron, with one p valence electron left for forming a weak Sn-Sn bond. According to the high-pressure single crystal X-ray diffraction measurements, no structural phase transition was observed up to ∼6.2 GPa. Temperature-dependent resistivity measurements up to 2.15 GPa on single crystals indicate that the phase-transition temperature occurring at the Néel temperature (TN) is significantly enhanced under high pressure. The robust crystallography and enhanced antiferromagnetic transition temperatures can be rationalized by the electronic structure calculations and chemical bonding analysis. The increasing Eu-P bonding interaction is consistent with the lattice parameter changing and enhanced TN. Moreover, the molecular orbital diagram shows that the weak Sn-Sn bond can be squeezed under pressure, acting as a compression buffer to stabilize the structure.

Cr2.37Ga3Se8: A Quasi-Two-Dimensional Magnetic Semiconductor.

We present a novel magnetic semiconductor, Cr2.37Ga3Se8, synthesized by partially replacing magnetic Cr3+ in antiferromagnetic Cr5+δSe8 with nonmagnetic Ga3+. The crystal structure of Cr2.37Ga3Se8 was determined by both powder and single-crystal X-ray diffraction. The title compound crystallizes in a monoclinic structure with space group C2/ m (No. 12). In Cr2.37Ga3Se8, the Cr atoms are surrounded by 6 Se atoms and form filled octahedral clusters, while Ga atoms are centered in the Se4 tetrahedral clusters. The two kinds of clusters pack alternatingly along the c-axis, which results in a quasi-two-dimensional layered structure. The magnetization ( M) measurement shows the development of short-range ferromagnetic coupling below the Curie-Weiss (CW) temperature θCW ∼ 92 K, evidenced by the nonlinear field dependence of M. However, the magnetic susceptibility exhibits a peak at low fields at ∼18 K, indicating the existence of an antiferromagnetic interaction as well. Electronic structure calculations using the WIEN2k program in the local spin density approximation indicate that the magnetism arises exclusively from local moments of the Cr atoms. The electrical resistivity measurement of the Cr2.37Ga3Se8 sample confirms that this material is a semiconductor with the band gap ∼0.26 eV. Meanwhile, the experimental band gap (∼0.26 eV) is close to the theoretical prediction using the WIEN2k program (∼0.35 eV).

Zintl Ions within Framework Channels: The Complex Structure and Low-Temperature Transport Properties of Na4Ge13.

Single crystals of a complex Zintl compound with the composition Na4Ge13 were synthesized for the first time using a high-pressure/high-temperature approach. Single-crystal diffraction of synchrotron radiation revealed a hexagonal crystal structure with P6/m space group symmetry that is composed of a three-dimensional sp3 Ge framework punctuated by small and large channels along the crystallographic c axis. Na atoms are inside hexagonal prism-based Ge cages along the small channels, while the larger channels are occupied by layers of disordered sixfold Na rings, which are in turn filled by disordered [Ge4]4- tetrahedra. This compound is the same as "Na1-xGe3+z" reported previously, but the availability of single crystals allowed for more complete structural determination with a formula unit best described as Na4Ge12(Ge4)0.25. The compound is the first known example of a guest-host structure where discrete Zintl polyanions are confined inside the channels of a three-dimensional covalent framework. These features give rise to temperature-dependent disorder, as confirmed by first-principles calculations and physical properties measurements. The availability of single-crystal specimens allowed for measurement of the intrinsic low-temperature transport properties of this material and revealed its semiconductor behavior, which was corroborated by theoretical calculations.