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Abstract: Flexible metal‐organic frameworks (MOFs) show large structural flexibility as a function of temperature or (gas)pressure variation, a fascinating property of high technological and scientific relevance. The targeted design of flexible MOFs demands control over macroscopic thermodynamics as determined by microscopic chemical interactions and remains an open challenge. Here we apply high‐pressure powder X‐ray diffraction and molecular dynamics simulations to gain insight into the microscopic chemical factors that determine the high‐pressure macroscopic thermodynamics of two flexible pillared‐layer MOFs. For the first time we identify configurational entropy that originates from side chain modifications of the linker as the key factor determining the thermodynamics in a flexible MOF. The study shows that configurational entropy is an important yet largely overlooked parameter, providing an intriguing perspective of how to chemically access the underlying free energy landscape in MOFs.

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Abstract: The occurrence and characterization of a new member of the dundasite group are reported. Grguricite, ideally CaCr2(CO3)2(OH)4·4H2O, is the Cr-analogue of alumohydrocalcite, CaAl2(CO3)2(OH)4·4H2O and occurs as lilac crusts of very fine-grained crystalline aggregates in the Pb-Ba-V mineralization found at the Adeghoual Mine, Mibladen, Morocco (32°46′0′′ N, 4°37′59′′ W). The identification was based upon a close match with the X-ray powder diffraction data for alumohydrocalcite, the confirmation of anion components identified by Raman spectroscopy and the cation composition determined by electron-probe microanalysis. The empirical formula based upon 14 oxygen atoms per formula unit is Ca0.84Pb0.03Cr1.65Al0.39Mg0.02(CO3)2(OH)4·4H2O, with carbonate, hydroxyl and water contents set to those of the alumohydrocalcite stoichiometry. The fine-grained nature of the crystals (c. 0.5 x 0.1 x 5 μm) precluded a single-crystal X-ray study and both density and optical determinations. Grguricite is triclinic with space group P1 ̄. Unit-cell parameters refined from the powder diffraction data are: a = 5.724(2) Å, b = 6.5304(9) Å, c = 14.646(4) Å, α = 81.682(1)°, β = 83.712(2)°, γ = 86.365(2)°, V = 537.8(2) Å3, Z = 2. The five strongest peaks in the powder pattern are [dhkl , I/Imax, (hkl)]: [6.222, 100, (011)], [3.227, 87, (020)], [6.454, 63, (010)], [2.883, 58, (005, 023, 121)], [7.208, 45, (002)]. The mineral is named after Australian geologist Ben Grguric.

Open Access

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Abstract: The response of the metal–organic framework aluminum-1,4-cyclohexanedicarboxylate or Al-CAU-13 (CAU: Christian Albrecht University) to the application of thermal and mechanical stimuli was investigated using synchrotron powder X-ray diffraction (SPXRD). Variable temperature in situ SPXRD data, over the range 80–500 K, revealed a complex evolution of the structure of the water guest containing Al-CAU-13•H2O, the dehydration process from ca. 310 to 370 K, and also the evolution of the guest free Al-CAU-13 structure between ca. 370 and 500 K. Rietveld refinement allowed this complexity to be rationalized in the different regions of heating. The Berman thermal Equation of State was determined for the two structures (Al-CAU-13•H2O and Al-CAU-13). Diamond anvil cell studies at elevated pressure (from ambient to up to ca. 11 GPa) revealed similarities in the structural responses on application of pressure and temperature. The ability of the pressure medium to penetrate the framework was also found to be important: non-penetrating silicone oil caused pressure induced amorphization, whereas penetrating helium showed no plastic deformation of the structure. Third-order Vinet equations of state were calculated and show Al-CAU-13•H2O is a hard compound for a metal–organic framework material. The mechanical response of Al-CAU-13, with tetramethylpyrazine guests replacing water, was also investigated. Although the connectivity of the structure is the same, all the linkers have a linear e,e-conformation and the structure adopts a more open, wine-rack-like arrangement, which demonstrates negative linear compressibility (NLC) similar to Al-MIL-53 and a significantly softer mechanical response. The origin of this variation in behavior is attributed to the different linker conformation, demonstrating the influence of the S-shaped a,a-conformation on the response of the framework to external stimuli.

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Abstract: High pressure X-ray diffraction, Raman scattering, and electrical measurements, together with theoretical calculations, which include the analysis of the topological electron density and electronic localization function, evidence the presence of an isostructural phase transition around 2 GPa, a Fermi resonance around 3.5 GPa, and a pressure-induced decomposition of SnSb2Te4 into the high-pressure phases of its parent binary compounds (α-Sb2Te3 and SnTe) above 7 GPa. The internal polyhedral compressibility, the behavior of the Raman-active modes, the electrical behavior, and the nature of its different bonds under compression have been discussed and compared with their parent binary compounds and with related ternary materials. In this context, the Raman spectrum of SnSb2Te4 exhibits vibrational modes that are associated but forbidden in rocksalt-type SnTe; thus showing a novel way to experimentally observe the forbidden vibrational modes of some compounds. Here, some of the bonds are identified with metavalent bonding, which were already observed in their parent binary compounds. The behavior of SnSb2Te4 is framed within the extended orbital radii map of BA2Te4 compounds, so our results pave the way to understand the pressure behavior and stability ranges of other “natural van der Waals” compounds with similar stoichiometry.

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Abstract: Angle-dispersive x-ray powder diffraction experiments have been performed on samarium metal up to 222 GPa. Up to 50 GPa we observe the Sm type (hR9) → dhcp (hP4) → fcc (cF4) → distorted fcc (hR24) → hP3 transition sequence reported previously. The structure of the high-pressure phase above 93 GPa, previously reported as having a monoclinic structure with space group C2/m, is found to be orthorhombic, space group Fddd, with eight atoms per unit cell (oF8 in Pearson notation). This structure is the same as that found in Am, Cm, and Cf at high pressures. Analysis of samarium's equation of state reveals marked changes in compressibility in the hP3 and oF8 phases, with the compressibility of the oF8 phase being that of a “regular” metal.