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As one of the most abundant materials in the world, calcium carbonate, CaCO3, is the main constituent of the skeletons and shells of various marine organisms. It is used in the cement industry and plays a crucial role in the global carbon cycle and formation of sedimentary rocks. For more than a century, only three polymorphs of pure CaCO3-calcite, aragonite, and vaterite-were known to exist at ambient conditions, as well as two hydrated crystal phases, monohydrocalcite (CaCO3·1H2O) and ikaite (CaCO3·6H2O). While investigating the role of magnesium ions in crystallization pathways of amorphous calcium carbonate, we unexpectedly discovered an unknown crystalline phase, hemihydrate CaCO3·½H2O, with monoclinic structure. This discovery may have important implications in biomineralization, geology, and industrial processes based on hydration of CaCO3.

The new microporous metal organic framework [La2(H2O)5(H2TPPE)]·3H2O (CAU‐54), is obtained in a hydrothermal reaction of the linker 1,1,2,2‐tetrakis(4′‐phosphonophenyl)ethylene (H8TPPE) and La3+ ions. The extensive characterization including temperature‐dependent crystal structures and spectroscopic properties allowed to understand the unique, multi‐responsive material properties. CAU‐54 exhibits rarely observed reversible photochromism as well as turn‐on photoluminescence by various external chemical or physical stimuli including change of pressure, solvent exchange, and temperature variation. These properties can be unequivocally assigned to the presence of tetraphenylethylene (TPE) moieties of the linker molecules within the MOF, i.e., the ordered spatial arrangement of the linker molecules, the presence of accessible pores as well as the coordination flexibility of the phosphonate groups and the rotational freedom of the linker. By temperature‐dependent steady‐state and time‐resolved luminescence studies, it is shown that this compound exhibits a) blue fluorescence that becomes effectively quenched at room temperature, b) green efficient luminescence with thermal stability up to 400 K, and c) red phosphorescence correlated to the observed photochromism. In addition, CAU‐54 shows unusual thermal expansion properties as shown by temperature‐dependent powder X‐ray diffraction measurements with identified transition points that correlate with the observed temperature‐dependent changes in the photoluminescence. [ABSTRACT FROM AUTHOR]

Hygroscopic single crystals of a new hexagonal high‐temperature modification of Sr[ReO4]2 were prepared from a melt of Sr[ReO4]2 ⋅ H2O and SrCl2 ⋅ 6 H2O. The structure analysis of the obtained crystals by X‐ray diffraction revealed that the title compound crystallizes in the ThCd[MoO4]3‐type structure with the hexagonal space group P63/m and the lattice parameters a=1023.81(7) pm and c=646.92(4) pm (c/a=0.632) for Z=2 in its quenchable high‐temperature form. Two crystallographically independent Sr2+ cations are coordinated by oxygen atoms forming either octahedra or tricapped trigonal prisms, whereas the Re7+ cations are found in the centers of discrete tetrahedral meta‐perrhenate units [ReO4]−. Temperature‐dependent in‐situ PXRD studies of dry powder samples of Sr[ReO4]2 exhibited its thermal dimorphy with a phase‐transition temperature at 500–550 °C from literature‐known m‐Sr[ReO4]2 into the newly discovered h‐Sr[ReO4]2 (hexagonal). [ABSTRACT FROM AUTHOR]

Hygroscopic single crystals of a new hexagonal high‐temperature modification of Sr[ReO4]2 were prepared from a melt of Sr[ReO4]2 ⋅ H2O and SrCl2 ⋅ 6 H2O. The structure analysis of the obtained crystals by X‐ray diffraction revealed that the title compound crystallizes in the ThCd[MoO4]3‐type structure with the hexagonal space group P63/m and the lattice parameters a=1023.81(7) pm and c=646.92(4) pm (c/a=0.632) for Z=2 in its quenchable high‐temperature form. Two crystallographically independent Sr2+ cations are coordinated by oxygen atoms forming either octahedra or tricapped trigonal prisms, whereas the Re7+ cations are found in the centers of discrete tetrahedral meta‐perrhenate units [ReO4]−. Temperature‐dependent in‐situ PXRD studies of dry powder samples of Sr[ReO4]2 exhibited its thermal dimorphy with a phase‐transition temperature at 500–550 °C from literature‐known m‐Sr[ReO4]2 into the newly discovered h‐Sr[ReO4]2 (hexagonal). [ABSTRACT FROM AUTHOR]

The synthesis and structural analysis of three new chloride-containing lithium thiophosphates(V) Li4Ln[PS4]2Cl with trivalent lanthanoids (Ln = Pr, Nd and Sm) are presented and discussed. Single crystals of Li4Sm[PS4]2Cl were obtained and used for crystal structure determination by applying X-ray diffraction. The other compounds were found to crystallize isotypically in the monoclinic space group C2/c. Thus, Li4Sm[PS4]2Cl (a = 2089.31(12) pm, b = 1579.69(9) pm, c = 1309.04(8) pm, β = 109.978(3)°, Z = 12) was used as a representative model to further describe the crystal structure in detail since Li4Pr[PS4]2Cl and Li4Nd[PS4]2Cl were confirmed to be isotypic using powder X-ray diffraction measurements (PXRD). In all cases, a trigonal structure in the space group R 3 ¯ (e.g., a = 1579.67(9) pm, c = 2818.36(16) pm, c/a = 1.784, Z = 18, for Li4Sm[PS4]2Cl) displaying almost identical building units worked initially misleadingly. The structure refinement of Li4Sm[PS4]2Cl revealed bicapped trigonal prisms of sulfur atoms coordinating the two crystallographically distinct (Sm1)3+ and (Sm2)3+ cations, which are further coordinated by four anionic [PS4]3− tetrahedra. The compounds also contain chloride anions residing within channel-like pores made of [PS4]3− units. Eight different sites for Li+ cations were identified with various coordination environments (C.N. = 4–6) with respect to chlorine and sulfur. EDXS measurements supported the stoichiometric formula of Li4Ln[PS4]2Cl, and diffuse reflectance spectroscopy revealed optical band gaps of 2.69 eV, 3.52 eV, and 3.49 eV for Li4Sm[PS4]2Cl, Li4Nd[PS4]2Cl, and Li4Pr[PS4]2Cl, respectively. The activation energy for Li+-cation mobility in Li4Sm[PS4]2Cl was calculated as Ea(Li+) = 0.88 eV using BVEL, which indicates potential as a Li+-cation conductor. [ABSTRACT FROM AUTHOR]

The prevalent global energy crisis calls for searching viable pathways for generating green hydrogen as an alternative energy resource. Dye‐sensitized photocatalytic water splitting is a feasible solution to produce green hydrogen. However, identifying suitable catalysts has been one of the bottlenecks in driving dye‐sensitized photocatalysis efficiently. In this work, a new class of electrocatalysts is reported based on the layered Weyl semimetals MIrTe4 (M = Nb, Ta) for the Eosin Y (EY)‐sensitized hydrogen evolution reaction (HER). NbIrTe4 and TaIrTe4 exhibit HER activities of ≈18 000 and 14 000 µmol g−1 respectively, after 10 h of irradiation with visible light. Time‐dependent UV‐Vis spectroscopy and high‐pressure liquid chromatography coupled with mass spectrometry analysis shed light on the reaction dynamics and enable a deeper understanding of the observed trend in hydrogen evolution rates for MIrTe4. MIrTe4 semimetals outperform transition metal‐based Weyl semimetals in terms of catalytic HER activity using EY as photosensitizer and triethanolamine as the sacrificial agent. It is hypothesized that the topology‐related band inversion in MIrTe4 Weyl semimetals promotes a high density of M d‐states near the Fermi level, driving their high catalytic performance. This study introduces a new class of layered Weyl semimetals as efficient catalysts, and provides perspectives for designing topology‐enhanced catalysts. [ABSTRACT FROM AUTHOR]

The conversion of La2O3 with HCl, subsequent neutralization and precipitation using (NH4)2CO3 in an industrial process leads to the previously unknown La2(CO3)3 ⋅ 5H2O. The phase was characterized by X‐ray powder diffraction leading to an averaged crystal structure model, thermal analysis, vibrational and optical spectroscopy. La2(CO3)3 ⋅ 5H2O crystallizes in space group Pbca(61) with a=9.0167(4) Å, b=12,842(3) Å, c=9.6331(4) Å and V=1115.4(3) Å3. The structure consists of ∞2LaCO34/4+ ${{}_{{\rm { \infty }}}{}^{{\rm { 2}}}\left\{{\left({\rm { La}}{\left({{\rm { CO}}}_{{\rm { 3}}}\right)}_{{\rm { 4/4}}}\right)}^{{\rm { +}}}\right\}}$ zig zag layers and a highly disordered interlayer space occupied by water molecules and carbonate anions. Partially occupied water‐related oxygen positions theoretically allow for a flexible hydrate water content La2(CO3)3 ⋅ xH2O, with x ranging from 1.5 to 5.0. Although a strong structural relationship between La2(CO3)3 ⋅ 5H2O and La2(CO3)3 ⋅ 8H2O and similar substance properties were found, the title compound cannot be obtained by partial dehydration of the octahydrate. Instead, both lanthanum carbonate hydrates transform into strongly disordered La2(CO3)3 in a one‐step dehydration process. [ABSTRACT FROM AUTHOR]