Single Crystal Studies Research Articles

Nanoindentation study of PbMoO4 single crystals: mechanical properties and implications for applications

Abstract Nanomechanical properties of lead molybdate (PbMoO4) single crystal were investigated using nanoindentation measurements. The force-dependent Young’s modulus and hardness of PbMoO4 along the [100] direction was determined using the Oliver–Pharr method. As the applied force increased, hardness and young modulus values decreased. This behavior was referred to the indentation size effect (ISE). The force-dependent plots were analyzed using proportional specimen resistance model and true hardness value was determined as 1.84 GPa. As a result of increasing the applied force from 5 to 100 mN, the Young modulus decreased from 81.7 to 60.2 GPa. The dependencies of plastic and elastic deformation components were also reported in the present study. It was seen that plastic deformation is the dominant component. The findings suggest that PbMoO4 is relatively soft material and can be considered as a promising material for mechanical and optoelectronics applications that require revealed hardness and Young’s modulus values.

Phthalazine based hydrazone as potent radical scavenger: Synthesis, spectral characterization, single crystal X-ray diffraction, DFT studies, molecular docking, ADME, antioxidant and antimicrobial activity of (E)-1-(2-substitutedbenzylidene)phthalazine derivatives

Phthalazine based hydrazone as potent radical scavenger: Synthesis, spectral characterization, single crystal X-ray diffraction, DFT studies, molecular docking, ADME, antioxidant and antimicrobial activity of (E)-1-(2-substitutedbenzylidene)phthalazine derivatives

Synthesis, single crystal investigations, DFT studies, biological activities, DNA cytotoxicity and molecular docking studies of copper(II) complex derived from the new o-vanillin Schiff base ligand

A novel Schiff base derivative, (E)-N’-(2-hydroxy-3-methoxybenzylidene)-2-phenylacetohydrazide (HMPH, H2L), and its Cu(II) complex were synthesized through the direct condensation of o-vanillin with phenylacetichydrazide in ethanol under reflux conditions. The synthesized ligand was identified usingelemental analysis, Fourier transform infrared (FTIR) and ultraviolet–visible (UV–Vis.) spectroscopy. The structures of HMPH (C16H16N2O3)2 and its Cu(II) complex [Cu(L)(H2O)]·H2O (C16H16N2CuO4·H2O) were analysed by single crystal X-ray diffraction technique. The X-ray diffraction results showed that HMPH crystallised in an orthorhombic Pca21 space group with a Z value of 8, while [Cu(L)(H2O)]·H2O crystallised in a monoclinic C 2/c space group with the same z value. The Cu(II) ion is coordinated to the acetohydrazide ligands via hydrazone nitrogen, aceto oxygen (N(2) and O(1)) and hydroxyl O(2) atoms. In addition to the single crystal structures of HMPH and [Cu(L)(H2O)]·H2O, the optimised molecular structures, molecular electrostatic potential meps, molecular orbital energy values, and interactions between DNA bases and molecular structures are determined by DFT/B3LYP/6-311G(d, p) for HMPH and DFT/B3LYP/LanL2DZ for [Cu(L)(H2O)]·H2O. The copper complex was found to be more potent than the organic ligand in terms of antimicrobial activity, with a strong anti-biofilm effect even at low MIC values. The cytotoxicity of the synthesized compounds was investigated on MDA-MB-231 cell lines. The [Cu(L)(H2O)]·H2O complex was found to be more lethal than the HMPH ligand. Furthermore, molecular docking studies of HMPH and [Cu(L)(H2O)]·H2O with P. aeruginosa ATCC27853 (PDB ID: 6P8U) were presented to explain the observed antibacterial activity and the mechanism-of-action.

Correction to: Structural, mechanical and antimicrobial studies of GZnA single crystal via slow solvent evaporation process

Correction to: Structural, mechanical and antimicrobial studies of GZnA single crystal via slow solvent evaporation process

Synthesis, characterization, X-ray structure, and DFT calculations of Zn complex encompassing HLN2O ligand: Relevance in cytotoxicity and antifungal photodynamic therapy.

This article presents the synthesis, characterization, and X-ray crystallographic features of one new Zn complex derived from a Salen-type tridentate ligand (HLN2O). A single-crystal diffraction study determined the complex crystal structure, which confirms that it crystallizes in the orthorhombic space group P212121. The single-crystal structure is constructed using the unique mononuclear component [ZnLN2°] and supramolecular CH∙∙∙π type interaction, resulting in a 1D structure. The IR, HRMS, and NMR study also support the complex structure. The Zn metal centre has a distorted square pyramidal geometry with τ value of 0.49. The Hirshfeld surfaces and 2D fingerprint confirm predominant H…H (77.9 %) interactions, with minor H…O, H…C, and H…N (5.0 %, 4.9 %, and 0.2 %). DFT calculations employed the B3LYP-D3/Lanl2DZ class of theory. FMO/MEP explains the complex reactivity perspective, while IP (4.71 eV) and low EA (1.11 eV) suit biological applications. The bonding gateway was analysed using NBO/QTAIM-NCI and ELF-LOL plots. Cytotoxicity was assessed using the Trypan blue exclusion method and tested against the DLA cell line, showing effectiveness against the DLA cell and suggesting complex potential as an anticancer agent. Antifungal photodynamic therapy (APDT) explored that ligand and Zn complex have significant activity against C. albicans. Finally, molecular docking simulations substantiate the experimental findings.

GRASP Integrated 3D Plotter: GRIP.

In research on mesoscale structure and correlations, small-angle neutron scattering (SANS) is increasingly being employed to map fully three-dimensional distributions of scattered intensity at low momentum transfer. While traditionally SANS experiments and data analysis methods are designed to prioritize the determination of salient information in only one or two dimensions, the trend towards volumetric intensity mapping experiments calls for new software tools to assist with analyzing the resulting datasets. In this paper, we describe the development of a new software module, the GRASP Integrated 3D Plotter (GRIP). GRIP adds numerous features to GRASP, a widely used SANS analysis program that was written in MATLAB and developed at the Institut Laue-Langevin, France. The GRIP module provides multiple methods of three-dimensional SANS data visualization and new abilities to perform 1D and 2D cuts in various momentum-space coordinate systems, including reciprocal lattice units relevant for single-crystal studies. GRIP also includes the ability to fit diffraction peaks to a fully three-dimensional ellipsoidal Gaussian function to extract peak parameters including peak intensity, location and width, as well as a built-in calculator for estimating the resolution-deconvolved 3D coherence lengths in a sample. GRIP thus represents a significant addition to GRASP which extends the utility and application of SANS. Valuable advantages are provided, in particular, for 'small-angle neutron diffraction' studies of mesoscale correlations in single crystals, such as those due to incommensurate magnetic spin textures like spirals and topological skyrmion lattices.

Tetranuclear N-Heterocyclic Carbene Palladium Acetate—The Fast-Initiating Precatalyst of Suzuki Coupling

A tetranuclear N-heterocyclic palladium carbene acetate, characterised by a [Pd]/[NHC] = 2/1 ratio, was synthesised and shown to be catalytically active in Suzuki coupling. Single crystal XRD studies of the complex revealed its unprecedented geometry, with the presence of three coordinated palladium centres. The catalytic activity of the complex is significantly higher than that of analogues containing the same N-heterocyclic carbene ligand. Preliminary studies have been carried out to determine the catalytic properties of the complex.

High-Pressure Low-Temperature Study of LnCa4O(BO3)3 (Ln = Pr, Nd, Gd, Er, Tm).

We investigated the site-disorder and thermal expansion of LnCa 4 O(BO3)3 (Ln = Pr, Nd, Gd, Er, Tm) through a single crystal structural study conducted between 100 and 300 K. Additionally, a high-pressure synchrotron X-ray diffraction study at low temperatures was conducted to determine the compressibility of both ordered and disordered prototype oxyborate lanthanides, specifically NdCa4O(BO3)3 and ErCa4O(BO3)3. The study revealed distinct behaviors consistent with their respective ionic radii. Furthermore, satellite reflections at 50 K, along with the onset of a triple a-parameter in the Nd crystal, indicate that the ground state of this extensively studied family may be different from what was previously reported.

Novel benzohydrazide derivative as a potential anticarcinogenic agent for breast cancer: Synthesis, crystal structure, in vitro and in silico assessments

Polycyclic aromatic compounds (PACs) are a class of organic molecules known for their significant biological activity, including anticancer properties. These compounds often interact with biological macromolecules, making them crucial in the development of new therapeutic agents. In this study, we report a new benzohydrazide derivative, (E)-4-(hexyloxy)-N'-(1-(naphthalen-2-yl)ethylidene)benzohydrazide (2), which incorporates a naphthalene ring, a typical PAC, as a core structural element. The structure of the compound was analyzed using FTIR, 1H NMR, 13C NMR and elemental analysis. Moreover, single crystal X-ray crystallography studies demonstrated that the compound adapted monoclinic crystal system with C 2/c space group. In the crystal structure, the intermolecular N–H···O hydrogen bonds link the molecules into infinite chains along the b-axis direction. The dominant interactions formed in the crystal packing were found to be hydrogen bonding and van der Waals interactions according to the Hirshfeld surface (HS) analysis. The evaluation of energy frameworks showed that stabilization of the compound was dominated by dispersion energy contribution. The anticancer activity of the compound was tested by employing several cellular assays. The compound showed strong anticancer effects, with IC50 values of 85 µM for MCF7 cells and 115 µM for MDA-MB-231 cells, indicating dose-dependent suppression of cell viability, migration, and colony formation. Computational analyses indicated favorable binding of compound 2 to ERRγ and predicted good oral availability of the generated compound. Pathway analysis using KEGG pathways identified significant enrichment in pathways related to cancer. These results highlight the compound's promise as a potential treatment option for breast cancer, prompting further exploration in future studies.

Structural, mechanical and antimicrobial studies of GZnA single crystal via slow solvent evaporation process

Structural, mechanical and antimicrobial studies of GZnA single crystal via slow solvent evaporation process

Investigation on growth, structural, spectral, optical, thermal, third order nonlinear optical and DFT studies of dibenzoylmethane single crystal for photonic and optoelectronic applications

Investigation on growth, structural, spectral, optical, thermal, third order nonlinear optical and DFT studies of dibenzoylmethane single crystal for photonic and optoelectronic applications

Pyridine hydrazide glycoconjugate-based gelators: Facile synthesis and exploring their application in iodide sensing

Detection of iodide (I−) holds great importance because of its crucial role in various biological activities in the human body. However, its selective detection using small molecular systems has not been as well-explored as metal complex and metal-framework structures, which are expensive and difficult to synthesize. Here, we have reported the synthesis of a novel class of 4,6-O-protected sugar-pyridine hydrazide derivatives in an environmentally benign condition with moderate yield. The overall characterization was done using NMR, HRMS, single-crystal XRD, and DFT studies. Anomeric forms of the N-glucosylamines were assigned from NMR spectroscopy and single-crystal XRD studies. The selective sensing ability towards I− of the synthesized derivatives has been confirmed through colourimetry, UV–Vis and 1H NMR titration and gelation studies. The 4,6-O-butylidene derivatives 6(a–c) were utilized because of their better solubility for the selective detection of iodide ion in solution, whereas 4,6-O-benzylidene derivatives 7(a–c) were used for the same in gel state for their enhanced gelation ability. Furthermore, the morphology of the xerogels have been analyzed through SEM and the thermal ability has been determined by DSC spectra. The experimental studies suggest that the iodide anion takes part in self-assembly formation with the sugar-pyridine hydrazide derivatives through C–H···I− interaction, which, along with H-bonding, π–π stacking, van der Waal force of interaction enhances the gel formation.

Multi-Stage Optimization of Pore Size and Shape in Pore-Space-Partitioned Metal-Organic Frameworks for Highly Selective and Sensitive Benzene Capture.

Compared to exploratory development of new structure types, pushing the limits of isoreticular synthesis on a high-performance MOF platform may have higher probability of achieving targeted properties. Multi-modular MOF platforms could offer even more opportunities by expanding the scope of isoreticular chemistry. However, navigating isoreticular chemistry towards best properties on a multi-modular platform is challenging due to multiple interconnected pathways. Here on the multi-modular pacs (partitioned acs) platform, we demonstrate accessibility to a new regime of pore geometry using two independently adjustable modules (framework-forming module 1 and pore-partitioning module 2). A series of new pacs materials have been made. Benzene/cyclohexane selectivity is tuned, progressively, from 4.5 to 15.6 to 195.4 and to 482.5 by pushing the boundary of the pacs platform towards the smallest modules known so far. The exceptional stability of these materials in retaining both porosity and single crystallinity enables single-crystal diffraction studies of different crystal forms (as-synthesized, activated, guest-loaded) that help reveal the mechanistic aspects of adsorption in pacs materials.

Low-Temperature Electron Spin Resonance Study of MnPS3 Antiferromagnetic Single Crystal.

van der Waals MnPS3 compound belonging to the class of Néel-type antiferromagnets (AFM) has recently emerged as a promising two-dimensional material for spintronic applications. In this study, we report on the electron spin resonance (ESR) study of an MnPS3 single crystal across the Néel transition temperature (T N = 78 K) for the magnetic field applied in the directions parallel and perpendicular to the crystallographic c axis. Furthermore, the ESR angular dependence at a temperature near T N has been investigated. We observed multiple resonance modes with antiferromagnetic, ferromagnetic, and paramagnetic characters. In addition, we revealed the occurrence of complex spin-spin correlations and a magnetic-topological Berezinskii-Kosterlitz-Thouless (BKT) phase transition (i.e., bound vortex-antivortex pairs) at T BKT with T BKT/T N typically found in two-dimensional magnets.

The Gauche‐Effect in 1,2‐Bis(arylsulfonate)ethanes

AbstractWith an aim of obtaining a fundamental understanding of C−C bond conformation theory, the molecular structure of an ethane with electron‐withdrawing groups, 1,2‐bis(4‐methoxybenzene‐sulfonate)ethane, was elucidated. According to the general conformation rule for alkanes, which states that molecules adopt a stabilized structure to avoid steric repulsion, ethanes typically adopt anti‐conformation. However, the title compound exhibited gauche‐conformation, as revealed by a single crystal diffraction study. Theoretical studies also support this behavior. Natural Bond Orbital (NBO) analysis suggests that the orbital interaction between the σ*CO orbital, attributable to the sulfonate groups, and the adjacent σCH orbital stabilizes the gauche‐conformation. The authors conclude that the sulfonate group acts as a gauche‐effect synthon, which is widely applicable in organic chemistry.

Layered Coordination Polymers Based on the Cluster Complexes [Re<sub>6</sub>Q<sub>8</sub>(CN)<sub>6</sub>]<sup>4–</sup> (Q = S or Se) and Dimeric Cations {(Ag(Dppe))<sub>2</sub>(μ-Dppe)}<sup>2+</sup>

The reactions of salts of cluster anions [Re6Q8(CN)6]4– with the [Ag(CN)2]– dicyanoargentate anion in the presence of 1,2-bis(diphenylphosphino)ethane are studied. Two new coordination polymers, [{(Ag(Dppe))2 (µ-Dppe)}2{Re6S8(CN)6}]⋅H2O (I) and [{(Ag(Dppe))2(µ-Dppe)}2{Re6Se8(CN)6}]0,85[{(Ag(Dppe))(Ag(DppeSe))(µ-Dppe)}2{Re6Se8(CN)6}]0,15 (II), are prepared by the solvothermal synthesis. The XRD study of single crystals of the compounds (CIF files CCDC nos. 2341356 (I) and 2341355 (II)) shows their layered structures. The XRD study of crystalline powders of the compounds shows that the synthesis of compound II leads to the formation of two crystalline phases, one of which is isostructural to compound I. The luminescence parameters of the solid-state compounds (quantum yields, emission lifetimes) resemble the parameters of other coordination polymers based on the [Re6Q8(CN)6]4– ions.

Synthesis, Characterization, Crystal structure determination and DFT study of a six coordinated Cu (II) complex of a phosphorous based tris-(2-pyridinylamino) phosphene sulphide ligand and its acid catalysed hydrolysis

One mono nuclear copper(II) complex (Cu-TPPS-OOCCH3 with structural formula C17H19CuN6O3PS) is synthesized using a novel tripodal tetradentate ligand, tris-(2-pyridinylamino)phosphene sulphide (TPPS), which has three pyridinylamino groups attached to a phosphorus atom connected to a sulphur atom (PS). The equatorial positions of the complex are occupied by three amino N-atoms of three aminopyridyl groups and one O-atom of the acetate group. The apical position is occupied by other O-atom of acetate group and one secondary N-atom of the tripodal ligand. The complex has been synthesized and purified as green solid and characterized by various spectroscopic techniques and the structure has been determined by X-ray single crystal diffraction study. The geometry optimizations and calculations of energies of the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) of the compounds are performed by using the hybrid B3LYP density functional theory (DFT) along with the def2TZVP basis set.

Application of enaminone ruthenium(II) complexes as catalysts in the transfer hydrogenation of ketones

This study reported the synthesis of two new ligands (1,2) and their Ru(II)-enaminone complexes (3,4). The Ru(II) complexes were obtained from the reaction of the [RuCl2(p-cymene)]2 dimers with the new enaminone derivative ligands (1,2). The use of standard spectroscopy techniques entirely characterized the compounds. Single crystal studies investigated the crystal structure of ligand (1) and complexes (3,4). X-ray diffraction data analysis was used to confirm the enaminone form of 1. Also, 3 and 4 exhibited the classical three-legged piano stool structure with Ru(II) coordinated by the nitrogen and oxygen atoms of 1 and a chloride ligand as the legs and the η6-π-bound p-cymene ligand occupies the seat of the piano stool. The Ru(II) complexes have been studied as catalysts in the transfer hydrogenation of acetophenone and other various ketones in the presence of KOtBu. The catalytic conditions were optimized using different substrate/catalyst and base/catalyst ratios. We found that the complexes show good activities and up to 100 % selectivity. The best turnover frequency (1667 h−1) was found for 3 when using acetophenone as the substrate.

Synthesis, single crystal study, molecular docking, and in vitro anticancer screening of a series of isoxazolone derivatives of 3-chloro-3-phenylacrylaldehydes

A series of isoxazole derivatives (2a-i) were synthesized by conventional method using various substituted 3-chloro-3-phenylacrylaldehydes as precursors. Structures of all the synthesized compounds were confirmed by spectroscopic data (1H NMR, FTIR, HRMS). Single crystal X-ray study of four compounds was carried out. Molecular docking study was performed and the compounds were screened for in vitro anticancer activity. The results show that compounds with no substituent or smaller substituents on benzene ring have significant antiproliferative activity against tested cell line i.e. MCF7.

Synthesis and Performance Evaluation of Zwitterionic C-N Bonded Triazole-Tetrazole-Based Primary Explosives.

Developing advanced metal-free nitrogen-enriched primary explosives is challenging due to the inherent risks associated with their synthesis and handling. However, there is an urgent need to develop novel lead-free, nitrogen-rich primary explosives that offer balanced energetic properties. C-N bonded bicyclic compound 3-azido-1-(1H-tetrazol-5-yl)-1H-1,2,4-triazol-5-amine (4), its salts, and 3,5-diazido-1H-1,2,4-triazole (8) were synthesized from inexpensive starting materials resulting in a fine blend of sensitivity and stability. These compounds exhibit high nitrogen content (79.78 to 83.43%), good thermal stability (129-210 °C), excellent detonation performance (VOD: 8592-9361 ms-1, DP: 27.1-33.8 GPa), and acceptable sensitivity (IS: 2.5-30 J, FS: 72-288 N). The hot needle tests of compounds 4 and 8 exhibit excellent ignition performance. All of the newly synthesized compounds were fully characterized using infrared spectroscopy (IR), high-resolution mass spectroscopy (HRMS), multinuclear magnetic spectroscopy (NMR), elemental analysis (EA), thermogravimetric analysis-differential scanning calorimetry (TGA-DSC), and 2, 4, and 8 were confirmed by single-crystal X-ray crystallographic studies. The molecular electrostatic potential (ESP), noncovalent interactions reduced density gradient (NCI-RDG) method, and QTAIM analysis were performed to investigate the intermolecular interactions. Together with promising performance properties, ease of synthesis, and ignitability, they are highly suitable candidates to pave new avenues for future applications.