Efficient Screening of Pharmaceutical Cocrystals by Microspacing In-Air Sublimation.

Cocrystal screening and single-crystal growth remain the primary obstacles in the development of pharmaceutical cocrystals. Here, we present a new approach for cocrystal screening, microspacing in-air sublimation (MAS), to obtain new cocrystals and grow high-quality single crystals of cocrystals within tens of minutes. The method possesses the advantages of strong designable ability of devices, user-friendly control, and compatibility with materials, especially for the thermolabile molecules. A novel drug-drug cocrystal of favipiravir (FPV) with salicylamide (SAA) was first discovered by this method, which shows improved physiochemical properties. Furthermore, this method proved effective in cultivating single crystals of FPV-isonicotinamide (FPV-INIA), FPV-urea, FPV-nicotinamide (FPV-NIA), and FPV-tromethamine (FPV-Tro) cocrystals, and the structures of these cocrystals were determined for the first time. By adjusting the growth temperature and growth distance precisely, we also achieved single crystals of 10 different paracetamol (PCA) cocrystals and piracetam (PIR) cocrystals, which underscores the versatility and efficiency of this method in pharmaceutical cocrystal screening.

Thermochromism Perovskite (COOH(CH2)3NH3)2PbI4 Crystals: Single-Crystal to Single-Crystal Phase Transition and Excitation-Wavelength-Dependent Emission.

As a potential multifunctional phase transition material, the organic-inorganic hybrid perovskite has attracted extensive attention in recent years. Here, we report the single-crystal to single-crystal phase transition and excitation-wavelength-dependent emission (EDE) of layered perovskite (COOH(CH2)3NH3)2PbI4. Single-crystal X-ray diffraction indicated that the crystal structure changes from layered Ruddlesden-Popper (RP) at 302 K to "X" network composed of face-sharing and corner-sharing [PbX6]4- octahedra at 425 K. The material exhibits thermochromic change from orange to yellow at higher temperature. Considering the thermochromism of the material, we apply it for anticounterfeiting and information encryption. The material exhibits EDE properties with a fluorescence color changing from green to red upon 420 and 546 nm excitation, respectively. Time-dependent density functional theory indicated that this phenomenon is mainly related to the laser-induced crystal structural transfer. Our research shows that the (COOH(CH2)3NH3)2PbI4 crystal has a potential application for multifunctional devices.

Low-Dimensional Hybrid Lead Iodide Perovskites Single Crystals via Bifunctional Amino Acid Cross-Linkage: Structural Diversity and Properties Controllability.

Three-dimensional perovskite AMX3 has great potential in photoelectric applications, but the poor stability is a major problem that restricts its practical application. The emergence of lower dimensional perovskite solves this problem. Here, we have synthesized a group of novel low-dimensional perovskites with diverse structures. Different amino acids were incorporated in the perovskite cage. The formulas of the compounds are (A')mPbIm+2 (A' = COOH(CH2)nNH2, n = 1, 3, 5, 7, 9). These families of materials demonstrate structure-related stability, tunable bandgap, and different photoluminescence. Single-crystal X-ray diffraction indicated that the five materials employ different structure types varying from edge-sharing structures to face- and corner-sharing Pb/I structures by adjusting the number of C atoms in organic cations, and the level of [PbI6]4- octahedral distortion was also identified. The film prepared using these materials with longer carbon chains (n = 5, 7, 9) showed better stability, and they did not decompose within one year at 75% RH, 40 °C. The bifunctional organic ions containing carboxyl groups as spacer cations will form additional hydrogen bonding between perovskite layers, resulting in higher stability of the material. The band gaps of these materials vary from 2.19 to 2.6 eV depending on the octahedral connection mode and [PbI6]4- octahedral distortion level, density functional theory calculations (DFT) are consistent with our experimental trends and suggest that the face-sharing structure has the maximum band gap due to its flatter electron band structure. Bright green fluorescence was observed in (COOH(CH2)7NH3)2PbI4 and (COOH(CH2)9NH3)2PbI4 when excited by 365 nm UV light. A thorough comprehension of the structure-property relationships is of great significance for further practical applications of perovskites.

Crystal Structures and Vapor-Induced Crystalline Transformation of 7-Ethyl-10-Hydroxycamptothecin Pseudopolymorphs.

Solvent-induced 3 frameworks (the monohydrate, methanol solvate, and dimethyl formamide [DMF] solvate) of an anticancer drug, 7-ethyl-10-hydroxycamptothecin (SN38), were constructed. The crystal structures of the 3 pseudopolymorphs were characterized by single-crystal X-ray diffraction technique for the first time. Crystal structure analysis of all these polymorphs revealed that the monohydrate showed 3D frameworks linked by hydrogen bonds. In the methanol solvate, the 1D molecular chains were linked by the methanol molecules through intermolecular hydrogen bonds to form a 2D sheet. The DMF solvate exhibits the 1D hydrogen bonding-linked chains along b-axis. Vapor-induced transformation has been investigated for the monohydrate, the methanol solvate, and the DMF solvate. The conversion relationships among the 3 solid frameworks are illustrated. Insights regarding transformation mechanisms have been established from consideration of the crystal structures.