Space Group C2 Research Articles

Uranium Oxide Hydrate Frameworks with Dy(III) or Lu(III) Ions: Insights Into the Framework Structures With Lanthanide Ions.

Two uranium oxide hydrate frameworks (UOHFs) with either Dy3+ or Lu3+ ions, Dy1.36(H2O)6[(UO2)10UO13(OH)4] (UOHF-Dy) or Lu2(H2O)8[(UO2)10UO14(OH)3] (UOHF-Lu), were synthesized hydrothermally and characterized with a range of structural and spectroscopic techniques. Although SEM-EDS analysis confirmed the same atomic ratio of ~5.5 for U : Dy and U : Lu, they displayed different crystal morphologies, needles for UOHF-Dy in the orthorhombic C2221 space group and plates for UOHF-Lu in the triclinic P-1 space group. Both frameworks are composed of β-U3O8 type layers linked by pentagonal bipyramidal uranium polyhedra, with the Dy3+/Lu3+ ions inside the channels. However, the arrangements of Dy3+/Lu3+ ions are different, with disordered Dy3+ ions well aligned at the centers of the channels and single Lu3+ ions well-separated in a zigzag pattern in the channels. While the characteristic vibrational modes were revealed by Raman spectroscopy, the presence of a pentavalent uranium center in UOHF-Lu was confirmed with diffuse reflectance spectroscopy. The formation of two types of UOHFs with lanthanide ions, high or low symmetry, and the structure trend were discussed regards to synthesis conditions and lanthanide ionic radius. This work highlights the complex chemistry driving the formation of UOHFs with lanthanide ions and has implications to the spent nuclear fuel under geological disposal.

A Highly Electrostrictive Salt Cocrystal and the Piezoelectric Nanogenerator Application of Its 3D-Printed Polymer Composite.

Ionic cocrystals with hydrogen bonding can form exciting materials with enhanced optical and electronic properties. We present a highly moisture-stable ammonium salt cocrystal [CH3C6H4CH(CH3)NH2][CH3C6H4CH(CH3)NH3][PF6] ((p-TEA)(p-TEAH)·PF6) crystallizing in the polar monoclinic C2 space group. The asymmetry in (p-TEA)(p-TEAH)·PF6 was induced by its chiral substituents, while the polar order and structural stability were achieved by using the octahedral PF6- anion and the consequent formation of salt cocrystal. The ferroelectric properties of (p-TEA)(p-TEAH)·PF6 were confirmed through P-E loop measurements. Piezoresponse force microscopy (PFM) enabled the visualization of its domain structure with characteristic "butterfly" and hysteresis loops associated with ferro- and piezoelectric properties. Notably, (p-TEA)(p-TEAH)·PF6 exhibits a large electrostrictive coefficient (Q33) value of 2.02 m4 C-2, higher than those found for ceramic-based materials and comparable to that of polyvinylidene difluoride. Furthermore, the composite films of (p-TEA)(p-TEAH)·PF6 with polycaprolactone (PCL) polymer and its gyroid-shaped 3D-printed composite scaled-up device, 3DP-Gy, were prepared and evaluated for piezoelectric energy-harvesting functionality. A high output voltage of 22.8 V and a power density of 118.5 μW cm-3 have been recorded for the 3DP-Gy device. Remarkably, no loss in voltage outputs was observed for the (p-TEA)(p-TEAH)·PF6 devices even after exposure to 99% relative humidity, showcasing their utility under extremely humid conditions.

Chiral Heterometallic Cu8Ln4 Complexes with Enantiopure Schiff Base Ligands: Synthesis, Structural, Spectroscopic and Magnetic Studies.

The enantiomerically pure Schiff base ligands H2L-S and H2L-R yield chiral heterometallic dodecanuclear complexes of the form [Cu8Ln4(OH)8(OMe)4(O2CBut)8(L-S or L-R)4(H2O)4] where LnIII=Gd (1S), Tb (2S), Dy (3S, 3R), Ho (4S, 4R), Er (5S) or Y (6S, 6R) and H2L=(S or R)-2-{[(1-hydroxypropan-2-yl)imino]methyl}-6-methoxyphenol. The complexes are isomorphous and crystallize in the non-centrosymmetric polar space group C2 in enantiomeric conformation. The chirality of the Schiff base ligands originates from the respective S- or R- enantiomer of 2-aminopropan-1-ol, is imparted to the complexes and to the crystals that belong to non-centrosymmetric space group. The chirality and enantiomeric conformation of all complexes are retained in dmso solutions as confirmed by Circular Dichroism spectra which consist of mirror images, expected for enantiomeric pairs. All complexes consist of four distorted cubane-like subunits [Cu2Ln2(μ3-OH)2(μ3-OMe)(μ3-OR)], which share the LnIII ions and result in a cyclic distorted tetragonal arrangement; each edge of the {LnIII 4} quadrilateral is occupied by two μ-OH- ions that further bridge to a CuII ion. Magnetic susceptibility measurements revealed ferromagnetic interactions for 3S with LnIII=Dy and antiferromagnetic interactions for all other complexes. AC susceptibility data of 3S under 1 kOe external dc field indicate slow magnetic relaxation phenomena below 2 K.

An innovative form of the essential trace element copper for fortification of dairy products

Microelementosis is a disease associated with a deficiency of certain vital microelements. Today, there are ways to combat the lack of essential micronutrients. In this article, the mechanochemical synthesis of a triple copper-containing complex with ascorbic acid and L-isoleucine, an essential amino acid, was carried out. Examination of the sample by X-ray diffractometry showed that the sample has a trigonal crystal structure with space group P31c. As a result of computer quantum chemical modeling, the values of the difference in total energy, chemical hardness, energy of the highest occupied molecular orbital and the lowest unoccupied molecular orbital were determined. We determined the optimal option for the interaction of copper with vitamin C and L-isoleucine, where the binding occurs through hydroxyl groups attached to the C2 and C3 atoms of ascorbic acid, and through the carboxyl group and α-amino group of isoleucine. The sample was examined by IR spectroscopy and confirmed by computer modeling data. The stability of the resulting complex was studied depending on the technological parameters — pH, temperature and exposure time. Using the Greco-Latin square method, a matrix for planning a multifactorial experiment was compiled. An analysis of the dependence of the change in optical density (∆ D) on pH, temperature and exposure time showed that the pH of the medium and the temperature of the solution have a significant effect on ∆ D: an increase in the pH of the medium and the temperature of the solution leads to an increase in ∆ D. Exposure time does not have a significant effect to change the optical density value (∆ D). The parameters at which sample stability is observed correspond to the lowest values of ∆ D: pH = 3–8, t = 25–70, τ = 5–15. The effect of the concentration of a copper-containing complex on the physicochemical parameters of milk was studied. It has been established that the optimal concentration of copper ascorbate isoleucinate for fortifying dairy products is 0.005 mol/l or less. Next, an organoleptic assessment of the indicators of milk enriched with copper ascorbate isoleucinate was carried out. The analysis of the results showed that the organoleptic parameters (smell and taste) of milk enriched with ascorbate-isoleucinate of copper are 0.1 points higher than those of milk enriched with the inorganic form of the essential trace element copper and 0.3 points lower than that of the control milk sample.

High-pressure/high-temperature synthesis, single-crystal structure analysis, and spectroscopic data of γ-Eu(BO2)3 and γ-Gd(BO2)3

Abstract Orthorhombic crystals of the compounds γ-Eu(BO2)3 and γ-Gd(BO2)3 were obtained by high-pressure/high-temperature syntheses at 10.5 GPa and 1100 and 900 °C, respectively. The structures were solved by single-crystal X-ray diffraction methods. The two compounds crystallize with four formula units per cell in the space group Pca21 (no. 29) with the unit cell parameters a = 18.2729(7), b = 4.4076(2), c = 4.2505(1) Å (Ln = Eu), and a = 18.2591(6), b = 4.4055(1), c = 4.2477(1) Å (Ln = Gd). Their infrared spectra and the luminescence spectrum of γ-Eu(BO2)3 are discussed.

Crystal structure and Hirshfeld surface analysis of 5-hy-droxy-penta-nehydrazide.

Carb-oxy-hydrazides are widely used in medicinal chemistry because of their medicinal properties and many drugs have been developed containing this functional group. A suitable inter-mediate to obtain potential hydrazide drug candidates is the title compound 5-hy-droxy-penta-nehydrazide, C5H12N2O2 (1). The aliphatic compound can react both via the hydroxyl and hydrazide moieties forming derivatives, which can inhibit Mycobacterium tuberculosis catalase-peroxidase (KatG) and consequently causes death of the pathogen. In this work, the hydrazide was obtained via a reaction of a lactone with hydrazine hydrate. The colourless prismatic single crystals belong to the ortho-rhom-bic space group Pca21. Regarding supra-molecular inter-actions, the compound shows classic medium to strong inter-molecular hydrogen bonds involving the hydroxyl and hydrazide groups. Besides, the three-dimensional packing also shows weak H⋯H and C⋯H contacts, as investigated by Hirshfeld surface analysis (HS) and fingerprint plots (FP).

Structure directing interactions in the crystals of o-hydroxyaryl/naphthyl derived aldimines: X-ray structure, Hirshfeld surface analysis, DFT and Molecular docking studies

We have synthesized and thoroughly analyzed many intermolecular interactions present in (E)-1-(((3-nitrophenyl)amino)methylene)naphthalen-2(1H)-one (a), (E)-5-(diethylamino)-2-(((3-nitrophenyl)imino)methyl)phenol(b) and (E)-2-(((3-nitrophenyl)imino)methyl)phenol (c). Compounds a (keto-amine tautomeric form) and b, which have one molecule in the asymmetric unit, crystallize in the monoclinic crystal system with space groups P21/n and C2/c, respectively. Compound C, on the other hand, crystallizes in an orthorhombic crystal structure with the space group Pca21. The structural analysis showed that the construction of ring motifs to stabilize the crystal packing involves several interactions, including pi stacking interactions, NH…O, and CH…O interactions. Hirshfeld surface analysis has been used to examine their solid-state structures, including the evaluation of several energy frameworks. The results show that hydrogen bonds play a major role in the formation of the molecular sheets, and that electrostatic energy contribution dominates stability. Using fingerprint plots, it was possible to examine the variations and commonalities in the target compounds' relative contributions from noncovalent interactions. In addition, B3LYP hybrid functional with 6- 311 G (d, p) level basis set was used in the density functional theory computations to optimize the structural coordinates. Through the examination of the molecular electrostatic potential surface, the chemically active areas of the target imine molecules were located. Additionally, using the internal ribosome entry site of the Hepatitis C virus ED42 (PDB-ID 3T4B), molecular docking of the title compounds was performed based on PASS analysis and literature findings.

Concentration and temperature dependence of Pr3+ f-f emissions in La(PO3)3

La(PO3)3 activated with different concentrations of Pr3+ was synthesized by a solid-state process. The obtained powder was composed of chunks of several microns in size, typical for this type of synthesis. X-ray diffraction confirmed an orthorhombic crystal structure with the C2221 space group. The electronic band structures and density of states of La(PO3)3 and La(PO3)3:Pr3+ are calculated and presented. The visible and near-infrared emissions from Pr3+ [Xe]4f2→ [Xe]4f2 electronic transitions were detected under 442 nm excitation. The red emission from the 1D2 state dominates visible spectra while emissions from the 3P0,1,2 states have smaller intensities. The 1D2 emission centered around 1020 nm is detected in the near-infrared spectral range. Intensities of 3P0 emissions increased with an increase in Pr concentration, while 1D2 emissions decreased in intensity. We found that the main process responsible for the 1D2 state decay is the Pr(1D2) + Pr(3H4) → Pr(1G4) + Pr(3F3,4) cross-relaxation between two Pr ions of electric dipole-dipole character. This finding is supported by 1D2 emission decay measurements, which revealed a reduction of average decay constants from 242 μs for a 0.5 mol% doped sample to 11 μs for a 10 mol% doped sample and an increasingly stronger non-exponential behavior of emission decay patterns with an increase in Pr3+ concentration.

Microwave-assisted combustion synthesis and characterization studies of novel dysprosium doped yttrium calcium borate (Dy3+: Y2CaB10O19) phosphor materials for efficient white light applications

Micro-wave assisted combustion synthesis technique was adopted to synthesize the dysprosium-doped yttrium calcium borate xDy3+: Y(2-x) CaB10O19 (Dy:YCB) polycrystalline phosphor materials with varying concentrations (x = 1, 3, 5, 7 and 9 mol %) for the first time. The formation of phase, crystal structure was analyzed by x-ray diffraction study and was affirmed to be formed pertaining to the monoclinic crystal structure (a = 11.475 Å, b = 6.345 Å, c = 9.223 Å and α = γ = 90°, β = 91.83°) with C2 space group. The absorption capability of the prepared samples was investigated by UV-DRS spectroscopy and the optical band gap was found to be 5.28 eV. FTIR study validated the presence of functional groups and their molecular vibrations. The excitation wavelength of the synthesized samples was found to be 350 nm from photoluminescence excitation (PLE) spectra. The PL emission spectra were recorded to authenticate the emission wavelengths and found to possess two emission peaks at 480 nm (blue) and 577 nm (yellow) contributed by the Dy3+ ions. The optimized dopant concentration of dysprosium ion was fixed at x = 0.07 to avoid the concentration quenching effect. The chromaticity co-ordinate of optimized sample was determined to be x = 0.3188, y = 0.3233 which are closer to ideal white light co-ordinate. The color temperature was determined to be 6209 K, which occurs in the cool white light region. Luminous efficacy of radiation (LER) was determined to be 269.31 l m/Wopt for the optimal phosphor. The luminous efficiency for the optimal phosphor was determined to be 40%. Color rendering index (CRI) of the optimal sample was evaluated to be 77. Internal quantum yield (IQE) of the optimal sample was determined to be 50.58 %. The phosphor materials have excellent thermal stability as validated from the temperature dependent PL measurements.

Accelerate the design of new superhard carbon allotropes in Pca21 space group: High-throughput screening and machine learning strategies

As an efficient calculation and screening method, high-throughput can discover and optimize new materials, shorten the development cycle and cost of new materials. However, using high throughput for material screening and computation, a large amount of computing resources and storage space are indispensable. To accelerate the design of novel superhard carbon materials, we combined machine learning methods with high-throughput computing to construct three machine learning models: support vector machine regression, random forests, and artificial neural networks, and mined data from existing material databases to select 1276 structures as datasets for the model to predict the volume modulus and shear modulus. Through comparative analysis, the optimal model was selected to predict the bulk modulus and shear modulus of the structures obtained by high-throughput calculations, and the prediction results of the model were verified by density functional theory (DFT) calculations, and 8 superhard carbon allotropes in the Pca21 space group were eventually found.

Radical Cation Salts of Hetera‐Buckybowls: Polar Crystals, Negative Thermal Expansion and Phase Transition

AbstractRadical cation salts of π‐conjugated polycycles are rich in physical properties. Herein, two kinds of hetera‐buckybowls, ethoxy‐substituted trithiasumanene (3SEt) and triselenasumanene (3SeEt), are synthesized as electron donors. Galvanostatic oxidation of them affords radical cation salts (3SEt)5(TTFMPB)3, (3SeEt)5(TTFMPB)3, (3SEt)4PMA, and (3SeEt)4PMA, where PMA is Keggin‐type phosphomolybdate and TTFMPB is tetrakis[3,5‐bis(trifluoromethyl)‐phenyl]borate. In these salts, 3SEt/3SeEt are partially charged and show distinct conformation change with the site charge and counter anions. In TTFMPB salts, (TTFMPB)− forms hexagonal channels that accommodate the packing columns of 3SEt/3SeEt. In particular, (3SEt)5(TTFMPB)3 adopts the R3c space group and is a polar crystal with the columns of 3SEt all in the up‐bowl direction. The PMA salts of 3SEt/3SeEt are polar crystals (C2 space group) with 3SEt/3SeEt being planar and forming columnar stacks. (3SeEt)4PMA shows a structural modulation below 200 K, namely, negative thermal expansion (NTE) of the unit cell volume and enlargement of the intermolecular distances between neighboring 3SeEt molecules. The four salts are semiconductors with an activation energy of 0.18–0.38 eV. The conductivity of (3SeEt)4PMA shows a reversible transition upon cooling and heating, in accordance to the NTE structural modulation. This work paves the way toward conducting materials based on hetera‐buckybowls.

Radical Cation Salts of Hetera-Buckybowls: Polar Crystals, Negative Thermal Expansion and Phase Transition.

Radical cation salts of π-conjugated polycycles are rich in physical properties. Herein, two kinds of hetera-buckybowls, ethoxy-substituted trithiasumanene (3SEt) and triselenasumanene (3SeEt), are synthesized as electron donors. Galvanostatic oxidation of them affords radical cation salts (3SEt)5 (TTFMPB)3 , (3SeEt)5 (TTFMPB)3 , (3SEt)4 PMA, and (3SeEt)4 PMA, where PMA is Keggin-type phosphomolybdate and TTFMPB is tetrakis[3,5-bis(trifluoromethyl)-phenyl]borate. In these salts, 3SEt/3SeEt are partially charged and show distinct conformation change with the site charge and counter anions. In TTFMPB salts, (TTFMPB)- forms hexagonal channels that accommodate the packing columns of 3SEt/3SeEt. In particular, (3SEt)5 (TTFMPB)3 adopts the R3c space group and is a polar crystal with the columns of 3SEt all in the up-bowl direction. The PMA salts of 3SEt/3SeEt are polar crystals (C2 space group) with 3SEt/3SeEt being planar and forming columnar stacks. (3SeEt)4 PMA shows a structural modulation below 200 K, namely, negative thermal expansion (NTE) of the unit cell volume and enlargement of the intermolecular distances between neighboring 3SeEt molecules. The four salts are semiconductors with an activation energy of 0.18-0.38 eV. The conductivity of (3SeEt)4 PMA shows a reversible transition upon cooling and heating, in accordance to the NTE structural modulation. This work paves the way toward conducting materials based on hetera-buckybowls.

Synthesis, characterization, and crystal structures of four 1,3-diisopropylbenzimidazolium salts with iodide, aluminum tetraiodide, tetrakis[3,5-bis(trifluoromethyl)-phenyl]borate, and triiodide anions

Four 1,3-disubstituted benzimidazolium salts: 1,3-diisopropylbenzimidazolium iodide (1), 1,3-diisopropylbenzimidazolium aluminum tetraiodide (2), 1,3-diisopropylbenzimidazolium triiodide (3), and 1,3-diisopropylbenzimidazolium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate (4) have been characterized using single X-ray diffraction analysis. Compounds 2–4 are new and are characterized by NMR and IR spectroscopy. Compound 2 was prepared by reacting 1 with aluminum triiodide and compound 4 in a metathesis reaction of 1 with sodium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate, giving yields of 96% and 93%, respectively. Compound 3 was prepared by reacting 1 with 1 eq. of iodine and was isolated in 34% yield. Compound 1 crystallizes in the Orthorhombic space group P212121 with an asymmetric unit consisting of one benzimidazolium cation and one iodine anion. Compound 2 crystallizes in the Monoclinic space group P21/ n with an asymmetric unit consisting of one benzimidazolium cation and one aluminum tetraiodide anion. Compound 3 crystallizes in the Monoclinic space group C2/ c with an asymmetric unit consisting of one and one-half benzimidazolium cations and one and one-half triiodide anions. Compound 4 crystallizes in the Triclinic space group P-1 with an asymmetric unit consisting of one benzimidazolium cation and one tetrakis[3,5-bis(trifluoromethyl)phenyl]borate anion. The NCN angles in all four compounds are approximately 110°, which is consistent with literature values. Stacking and halogen and hydrogen bonding interactions in the series are also discussed.

Photoinduced patterning of oxygen vacancies to promote the ferroelectric phase of Hf0.5Zr0.5O2

Photoinduced reductions in the oxygen vacancy concentration were leveraged to increase the ferroelectric phase fraction of Hf0.5Zr0.5O2 thin-films. Modest (∼2−77 pJ/cm2) laser doses of visible light (488 nm, 2.54 eV) spatially patterned the concentration of oxygen vacancies as monitored by photoluminescence imaging. Local, tip-based, near-field, nanoFTIR measurements showed that the photoinduced oxygen vacancy concentration reduction promoted formation of the ferroelectric phase (space group Pca21), resulting in an increase in the piezoelectric response measured by piezoresponse force microscopy. Photoinduced vacancy tailoring provides, therefore, a spatially prescriptive, post-synthesis, and low-entry method to modify phase in HfO2-based materials.

Naalasite, NaAl(AsO3OH)2⋅H2O, the Al analogue of nafeasite from the Torrecillas mine, Iquique Province, Chile

AbstractThe new mineral naalasite (IMA2023–027), NaAl(AsO3OH)2⋅H2O, was found at the Torrecillas mine, Iquique Province, Chile, where it is a secondary alteration phase associated with anhydrite, juansilvaite, magnesiokoritnigite and a lavendulan-like phase. Naalasite occurs in tightly intergrown aggregates and druses of equant crystals. Crystals are light to medium pink and transparent, with vitreous lustre and white streak. The Mohs hardness is ~3½. The density is 3.19(2) g⋅cm–3. Optically, naalasite is uniaxial (+), with ω = 1.630(3) and ɛ = 1.660(3) (white light). The empirical formula (based on 9 O apfu) is Na0.92Al0.61Fe3+0.39As2O9H4.07. Naalasite is trigonal, space group R32, with cell parameters: a = 8.494(4), c = 26.430(13) Å, V = 1651.5(4) Å3 and Z = 9. The structure, refined to R1 = 3.78% for 641 I > 2σI reflections, is based on a loose 3D framework of alternating AsO3OH tetrahedra and AlO6 octahedra. The structure is topologically equivalent to that of nafeasite and can be regarded as its Al analogue, even though nafeasite is monoclinic with space group C2.

From ZnF2 to ZnF2(H2O)4: Partial Substitution Achieves Structural Transformation and Nonlinear Optical Activity while Keeping Short Ultraviolet Cutoff Edge.

Exploring nonlinear optical (NLO) materials with short ultraviolet cutoff edges are significant for developing an all-solid-state laser. Here, a noncentrosymmetric zinc fluoride hydrate, ZnF2(H2O)4, was synthesized by a hydrothermal method. It crystallizes in the polar space group of Pca21. The compound consists of the central Zn2+ combined with F- and coordination water to form the [ZnF2(H2O)4] octahedra, and each octahedron is isolated from each other to form a 0-dimensional structure. As an acentric compound, ZnF2(H2O)4 shows a phase-matchable second-harmonic-generation (SHG) activity with an intensity about 0.5 times that of KH2PO4. More attractively, it also shows a short ultraviolet cutoff edge below 200 nm, which is rare in reported halide hydrate systems. Interestingly, from ZnF2 to ZnF2(H2O)4, the partial substitution of the coordinated F atoms by H2O molecules leads to the structural transformation from centric to acentric with SHG activity off to on. Structural analyses, NLO activity, and theoretical calculations are presented in this work.

Polar Organic Charge-Transfer Complex of the Asymmetrical Component for Flexible Piezoelectric Energy Harvesting and Self-Powered Wearable Sensors.

Organic piezomaterials have attracted much attention because of their easy processing, lightweight, and mechanic flexibility properties. Developing new smart organic piezomaterials is highly required for new-generation electronic applications. Here, we found a novel organic piezomaterial of organic charge-transfer complex (CTC) consisting of dibenzcarbazole analogue (DBCz) and tetracyanoquinodimethane (TCNQ) in the molecular-level heterojunction stacking mode. The DBCz-TCNQ complex exhibited ferroelectric properties (the saturated polarization of ∼1.23 μC/cm2) at room temperature with a low coercive field. The noncentrosymmetric alignment (Pc space group) led to a spontaneous polarization of this architecture and thus was the origin of the piezoelectric behavior. Lateral piezoelectric nanogenerators (PENGs) based on the thermal evaporated CTC thin-film exhibited significant energy conversion behavior under mechanical agitation with a calculated piezoelectric coefficient (d31) of ∼33 pC/N. Furthermore, such a binary CTC thin-film constructed single-electrode PENG could show steady-state sensing performance to external stimuli as this flexible wearable device precisely detected physiological signals (e.g., finger bending, blink movement, carotid artery, etc.) with a self-powered supply. This work provides that the polar CTCs can act as efficient piezomaterials for flexible energy harvesting, conversion, and wearable sensing devices with a self-powered supply, enabling great potential in healthcare, motion detection, human-machine interfaces, etc.

Nonlinear optical and spectroscopic properties, thermal analysis, and hemolytic capacity evaluation of quinoline-1,3-benzodioxole chalcone.

This article describes the synthesis, characterization (1H NMR, 13C NMR, FT-IR, HRMS and XRD), UV-Vis absorption and fluorescence spectra, theoretical analysis, evaluation of nonlinear optical properties (NLO), thermal analysis and determination of the hemolytic capacity of the compound (E)-N-(4-(3-(benzo[d][1,3]dioxol-5-yl)acryloyl)phenyl)quinoline-3-carboxamide (5). Radiological findings showed that compound 5 crystallized in space group Pca21. Furthermore, theoretical DFT studies performed with the B3LYP and M062X functionals showed good agreement with the experimental results and provided valuable information on the molecular and electronic structure, reactivity, polarizability, and kinematic stability of the compound. Besides, compound 5 did not show any hemolytic effect on human erythrocytes and exhibited strong NLO properties. The TG and DTA thermograms of quinoline-chalcone (5) revealed a multi-step thermal decomposition process with a total mass loss of 83.2%, including water content loss. The DTA curves exhibited endothermic peaks corresponding to decomposition steps, melting point, and thermochemical transition. Additionally, exothermic peaks in the DTA thermograms align with significant mass loss, confirming the compound's melting point and water content, as validated by X-ray diffraction analysis. These results contribute to the advancement of research on compounds with NLO properties and offer a promising avenue for the development of substances potentially applicable to optical devices in the biomedical field.

L-Cysteine oxalates with dimeric and trimeric cations

Single crystals of two new compounds, (l-CysH···l-Cys)(HC2O4) (I) and (l-CysH···l-Cys···l-CysH)(HC2O4)2·0.5H2O (II), were obtained. Crystal structures were solved and refined using single-crystal X-ray diffraction, and compared with the previously known orthorhombic and monoclinic modifications of the simple salt (l-CysH)(HC2O4). Compound (I) crystallizes in the triclinic crystal system (space group P1, Z=2) and contains (l-CysH···l-Cys) dimeric cations with very short O···O interatomic distance of 2.434(2) Å. Hydrogen oxalate anions form head-to-tail type chains with very short hydrogen bonds, characterized by O···O distances of 2.422(2) Å and 2.417(3) Å. The crystal lattice of (II) is monoclinic with the space group C2, Z=4. It contains a new type of cation, that has never been observed before for cysteine salts, i.e. trimeric (l-CysH···l-Cys···l-CysH) cation. Protonated l-cysteinium cations are connected to the zwitterionic l-cysteine moiety through the same oxygen atom of the carboxylate group via hydrogen bonds, with O···O distances of 2.6410(18) Å and 2.4888(19) Å. Similar to the structure (I), the hydrogen oxalate anions form head-to-tail type chains linked by short hydrogen bonds with O···O distances of 2.4369(17) Å and 2.4330(17) Å, respectively. The crystals were characterized by IR and Raman spectroscopy. The batches obtained on crystallization were also characterized by X-ray powder diffraction, in order to check the phase purity of all the sample.

Synthesis and structure-dependent optical properties of two new organic-inorganic hybrid antimony(III) chlorides.

Two organic-inorganic hybrid antimony(III) chlorides, namely (C9H26N3)2Sb4Cl18 (1) and (C9H26N3)SbCl6 (2), were prepared using a facile solvent evaporation method. They have low-dimensional structures constructed from SbCl6 octahedra and triply protonated N,N,N',N'',N''-pentamethyldiethylenetriamine cations. The organic cations exhibit different conformations in the two compounds. Compound 1 crystallizes in the centrosymmetric space group P1̄, while compound 2 crystallizes in the noncentrosymmetric space group Pca21. Notably, compound 2 exhibits a moderate second harmonic generation (SHG) response of about 1.3 times that of KH2PO4 (KDP) under 1064 nm laser irradiation. Meanwhile, this compound displays green-yellow luminescence under 342 nm ultraviolet light irradiation, indicating its potential as a bifunctional optical material. Theoretical calculations based on density functional theory were also performed to gain insights into the correlation between their structures and optical properties.