Ba5Ga2SiO4S6: a Phase-Matching Nonlinear Optical Oxychalcogenide Design via Structural Regulation Originated from Heteroanion Introduction.

Tailored structural regulation to obtain a new non-centrosymmetric (NCS) compound with excellent optical properties is highly desirable but remains a challenge for nonlinear optical (NLO) material design. In this work, centrosymmetric celsian-type BaGa2Si2O8 was selected as a template structure, and a novel NCS oxychalcogenide, namely, Ba5Ga2SiO4S6, was successfully designed via the introduction of heteroanions under high-temperature solid-state conditions. Ba5Ga2SiO4S6 adopts the monoclinic space group of Cc (no. 9) and is formed by charges balancing Ba2+ cations and discrete [Ga2SiO4S6] clusters made of corner-sharing [SiO4] and [GaOS3] tetrahedra. Notably, Ba5Ga2SiO4S6 exhibits the critical requirements as a potential UV NLO candidate, including a phase-matching second-harmonic generation intensity (∼1.0 × KDP), a beneficial laser-induced damage threshold (1.2 × KDP), a large birefringence (Δn = 0.10@546 nm), and a short UV absorption cutoff edge (ca. 0.26 µm). Furthermore, the theoretical calculation is implemented to provide a deeper analysis of the structure-activity relationship. The investigated example of structural regulation originated from heteroanion introduction in this study may offer a feasible strategy for high-performance NLO candidate design.

Quaternary Chalcohalides CdSnSX2 (X = Cl or Br) with Neutral Layers: Syntheses, Structures, and Photocatalytic Properties.

Inorganic chalcohalides are attracting a tremendous amount of attention because of their remarkable structural variety and desirable physical properties. Although great advances have been made in recent years, functional inorganic chalcohalides with two-dimensional neutral layers are still rare. Herein, two novel chalcohalides CdSnSX2 (X = Cl or Br) with high yields were obtained by reacting CdX2 with SnS using a traditional solid-state method at 823 K. Both of these chalcohalides adopt orthorhombic space group Cmcm (No. 63) with the following structural values: a = 4.014(4)-4.064(2) Å, b = 12.996(2)-13.746(3) Å, c = 9.471(2)-9.621(2) Å, V = 494.1(8)-537.5(2) Å3, and Z = 4. The prominent architectural feature is the unique two-dimensional [CdSnSX2] neutral layer consisting of composite [CdX2] and [SnS] sublattices that are connected alternately through the Cd-S-Sn bonds along the ac plane. The [CdX2] sublattice consists of a single octahedral chain of Cd-centered [CdX4S2] groups sharing cis-X edges, while the [SnS] sublattice consists of a bend-shaped chain of unusual [SnS2X2] units sharing vertices of S atoms. Significantly, each CdSnSX2 form (X = Cl or Br) shows high visible-light-induced photocatalytic activity for rhodamine B degradation, which is ∼7.0 times higher than that of nitrogen-doped TiO2 (TiO2-xNx) under the same experimental conditions. This discovery enriches the categories of inorganic chalcohalides and provides more choices of candidate materials for photocatalytic applications.

[(Ba19Cl4)(Ga6Si12O42S8)]: a Two-Dimensional Wide-Band-Gap Layered Oxysulfide with Mixed-Anion Chemical Bonding and Photocurrent Response.

Mixed-anion compounds play an essential part in modern structural chemistry. In this Communication, an unprecedented hexanary oxysulfide, [(Ba19Cl4)(Ga6Si12O42S8)] (FJ-1), was synthesized at 1073 K by a standard solid-state method, which is a new phase in the AE/MIII/MIV/O/Q/X (AE = alkaline-earth metal; MIII = group 13 metal; MIV = group 14 metal; Q = chalcogen; X = halogen) system. FJ-1 adopts a new structure type and crystallizes in the orthorhombic system with space group Cmcm. In the structure, unique two-dimensional [Ga6Si12O42S8]34- layers formed by the familiar [SiO4] species and unusual heteroligand [GaO2S2] and [GaO3S] tetrahedra extend the intralayer linking. Significantly, a photoelectrochemical test revealed that FJ-1 is photoresponsive under ultraviolet illumination. Moreover, density functional theory calculations were employed to gain insight into the relationship between the electronic structure and optical properties. Such work will be conducive to the structural diversity of gallium coordination chemistry by exploration of the new mixed-anion functional chalcohalides.

Ternary Mixed-Metal Cd4GeS6: Remarkable Nonlinear-Optical Properties Based on a Tetrahedral-Stacking Framework.

Noncentrosymmetric (NCS) mixed-metal chalcogenides have attracted significant attention lately because of their structural multiplicities, strong second-harmonic-generation (SHG) efficiencies ( d ij) and large laser-induced damage thresholds (LIDTs), which make them promising nonlinear-optical (NLO) materials in mid- and far-IR (MFIR) applications. In this work, a ternary mixed-metal material, Cd4GeS6, has been synthesized by reacting CdS with GeS2 via a solid-state method at 1273 K. It exhibits a unique tetrahedral-stacking NCS framework structure consisting of two types of [Cd2S7] asymmetric groups and dispersed GeS4 tetrahedra. Remarkably, Cd4GeS6 shows type-I phase-matching ability and achieves a desired balance between strong d ij (about 1.1AgGaS2) and large LIDT (about 3.6AgGaS2), demonstrating that this material satisfies the essential requirements as a promising MFIR NLO candidate. Moreover, theoretical calculations were performed for a better understanding of the structure-property relationships.

Post-marketing safety concerns with elagolix: a disproportionality analysis of the FDA adverse event reporting system.

OBJECTIVE: Elagolix is approved for the treatment of moderate-to-severe pain associated with endometriosis. However, the long-term safety of elagolix in a large sample of real-world patients is unknown. METHODS: The U.S. Food and Drug Administration Adverse Event Reporting System (FAERS) reports were collected and analyzed from January 2019 to June 2023. Disproportionality analyses, including the reporting odds ratio (ROR), the proportional reporting ratio (PRR), the Bayesian confidence propagation neural network (BCPNN), and the multi-item gamma Poisson shrinker (MGPS) algorithms, were employed in data mining to quantify the signals of elagolix-related adverse events (AEs). RESULTS: After removing the non-drug-related AE signals, we detected several AE signals such as hot flushes, bone pain, suicidal ideation, depression, and increased liver enzymes, which were known during the clinical trial phase. In addition to this, we detected several unexpected important AEs that were not mentioned in the drug insert, including cystitis interstitial, parosmia, and epiploic appendagitis. The median onset time of elagolix-associated AEs was 28.5 days. CONCLUSION: Our study provides a comprehensive picture of the safety of elagolix in the post-marketing setting, while also identifying potential new AE signals. These findings emphasize the importance of continued monitoring of the potential risks of elagolix.

An unprecedented pentanary chalcohalide with Mn atoms in two chemical environments: unique bonding characteristics and magnetic properties.

Mixed-anion chalcohalides have attracted significant attention lately, attributable to their unique structure compositions and captivating physicochemical properties. Herein, an unprecedented pentanary chalcohalide, Cs2[Mn2Ga3S7Cl] (1), was discovered by solid-state reaction at 1223 K. It is constructed by alternately stacked layers, each of which is made by a 2D [Ga3S9]9- ribbon embedded with 1D [Mn2S8Cl]13- chains. The coexistence of two Mn-coordinated polyhedra ([MnS6] octahedra and hetero-ligand [MnS3Cl] tetrahedra) in one material is surprisingly observed for the first time in the Mn-containing inorganic chalcogenides or chalcohalides. More interestingly, it exhibits ferrimagnetic (FIM) behaviour, which could be correlated to the magnetic sub-lattice sites with different coordination geometries. This work suggests a new route for designing and searching for unique functional chalcohalides with different chemical environments.