Growth, Structural, Spectral, Thermal, Optical, Second and Third Order Nonlinear Optical Properties of Imidazolium Hydrogen Squarate (IHS) Single Crystal

Imidazolium hydrogen squarate (IHS) crystal has been grown by slow evaporation solution growth technique at room temperature. The lattice parameters of grown crystal were determined using single crystal X-ray diffraction data and compared with powder XRD. Single crystal XRD shows that the crystal crystallizes in monoclinic system with noncentrosymmetric space group Pc. The crystallinity of the grown crystal was confirmed by X-ray powder diffraction analysis. FT-IR and FT-RAMAN analyses qualitatively confirm the various functional groups present in the grown crystal. The 1H and 13C NMR spectra were recorded to establish the molecular structure. Thermal properties of title crystal were studied by thermogravimetric analysis (TGA) and differential thermal analysis (DTA). The UV-Vis-NIR transmission spectrum was recorded to find the band width of optical transmittance window and the lower cutoff wavelength. The optical band gap value of the material is evaluated to be 5.6 eV. The second harmonic generation efficiency was calculated by the Kurtz and Perry powder method using a Q-switched mode locked Nd: YAG laser emitting 1064 nm laser as source. Finally, Z-scan technique was employed to determine the nonlinear refractive index, nonlinear absorption coefficient and third-order NLO susceptibility to find suitability of the grown crystal in photonics and optoelectronics applications. Keywords: Single crystal; Powder XRD; thermal analysis; SHG; Z-scan studies

A Comprehensive Experimental and Theoretical Study on the [{(η5-C5H5)2Zr[P(µ-PNEt2)2P(NEt2)2P]}2O Crystalline System

The structure of tetraphosphetane zirconium complex C52H100N8OP10Zr2 1 was determined by single crystal X-ray diffraction analysis. The crystal belongs to the monoclinic system, space group P21/c, with a = 19.6452(14), b = 17.8701(12), c = 20.7963(14)Å, α = γ = 90°, β = 112.953(7)°, V = 6722.7(8)Å3, Z = 4. The electronic structure of the organometallic complex has been characterized within the framework of Quantum Chemical Topology. The topology of the Electron Localization Function (ELF) and the electron density according to the Quantum Theory of Atoms in Molecules (QTAIM) show no covalent bonds involving the Zr atom, but rather dative, coordinate interactions between the metal and the ligands. This is the first reported case of a Zr complex stabilized by an oxide anion, anionic cyclopentadienyl ligands and rare tetraphosphetane anions.

Chemical Preparations and X-ray Diffraction Data of Cyclotriphosphates Type MnMII2(P3O9)2.nH2O with MII Alkaline Earths

Chemical preparation methods and X-ray powder diffraction data, XPRD, are reported for four cyclotriphosphates associated with manganese MnMII2(P3O9)2.nH2O with MII alkaline earths. These phosphates are MnCa2(P3O9)2.10H2O, MnCa2(P3O9)2, MnSr2(P3O9)2.4H2O and MnBa2(P3O9)2.6H2O. The condensed phosphates MnSr2(P3O9)2.4H2O and MnBa2(P3O9)2.6H2O were prepared by the method of ion-exchange resin, whereas MnCa2(P3O9)2.10H2O was prepared by using nitrates and MnCa2(P3O9)2 was obtained by total thermal dehydration of MnCa2(P3O9)2.10H2O. MnSr2(P3O9)2.4H2O crystallizes in the triclinic system, space group is P-1, Z = 1, the unit-cell parameters are : a = 6,653(1)Å, b = 7,110(1)Å, c = 5,123(1)Å, α = 103,37(2)°, β = 95,81(2)°, γ = 93,04(2)° and the factors of merit, M(20) = 29.6 and F(30) = 34.4. MnCa2(P3O9)2.10H2O crystallizes in the monoclinic system, space group is P21/n, the unit-cell parameters of MnCa2(P3O9)2.10H2O are : a = 9.631 (5) Å, b = 18.173 (7) Å, c = 7.976 (4) Å, β = 109.438 (4), Z = 2 and V = 1045,1 (3) Å3. MnCa2(P3O9)2 an hexagonal symetry, Z = 2, the space group is P3 and the unit-cell parameters are a = 7.392 Å (9) and c = 20.134 (2) Å. MnBa2(P3O9)2.6H2O crystallizes in the triclinic unit cell, , Z = 2, the space group is P-1 and its unit-cell parameters are : a = 7,479 (6)Å, b = 11,942 (8)Å, c = 12,786 (9)Å, α = 105,94(7)°, β = 98,40°(7), γ = 98,16 (7)° and V = 1046,8 (2)Å3.

Maximizing completeness in single-crystal high-pressure diffraction experiments: phase transitions in 2°AP

Sufficiently high completeness of diffraction data is necessary to correctly determine the space group, observe solid-state structural transformations or investigate charge density distribution under pressure. Regrettably, experiments performed at high pressure in a diamond anvil cell (DAC) yield inherently incomplete datasets. The present work systematizes the combined influence of radiation wavelength, DAC opening angle and sample orientation in a DAC on the completeness of diffraction data collected in a single-crystal high-pressure (HP) experiment with the help of dedicated software. In particular, the impact of the sample orientation on the achievable data completeness is quantified and proved to be substantial. Graphical guides for estimating the most beneficial sample orientation depending on the sample Laue class and assuming a few commonly used experimental setups are proposed. The usefulness of these guides has been tested in the case of luminescent 1,3-diacetylpyrene, suspected to undergo transitions from the α phase (Pnma) to the γ phase (Pn21 a) and δ phase (P1121/a) under pressure. Effective sample orientation has ensured over 90% coverage even for the monoclinic system and enabled unrestrained structure refinements and access to complete systematic extinction patterns.

DFT Calculation, Hirshfeld Analysis and X-ray Crystal Structure of Some Synthesized N-alkylated(S-alkylated)-[1,2,4]triazolo[1,5-a]quinazolines

The present work aimed to synthesize 2-methylthio-triazoloquinazoline derivatives and study their X-ray, NMR, DFT and Hirshfeld characteristics. The cyclocondensation of dimethyl-N-cyanodithiocarbonate with 2-hydrazinobenzoic acid hydrochloride resulted in an intermediate, 2-methylthio-[1,2,4]triazolo[1,5-a]quinazolin-5-one (A), which upon treatment with phosphorus pentasulfide, transformed into the 2-methylthio-[1,2,4]triazolo[1,5-a]quinazolin-5-thione (B). Reaction of 2-methylthio-triazoloquinazolines (A&B) with alkyl halides (allyl bromide and ethyl iodide) in basic medium afforded 4-allyl-2-methylthio-[1,2,4]triazolo[1,5-a]quinazolin-5-one (1; N-alkylated) and 5-ethylthio-2-methylthio-[1,2,4]triazolo[1,5-a]quinazoline (2; S-alkylated), respectively. Their molecular and supramolecular structures were presented. Unambiguously, the molecular structures of 1 and 2 were confirmed via NMR and single-crystal X-ray diffraction. The resulting findings confirmed the structures of 1 and 2 and determined their crystalized system (monoclinic system; P21/n space group). Hirshfeld analysis of 1 revealed the importance of the significantly short O…H (6.7%), S…S (1.2%) and C…C (2.8%); however, the short H···H (42.6%), S···H (16.3%) and C···C (4.3%) were showed in 2 by intermolecular interactions in the molecular packing. The 1,2,4-triazoloquinzolines (1&2) were anticipated to be relatively polar compounds with net dipole moments of 2.9284 and 4.2127 Debye, respectively. The molecular electrostatic potential, atomic charge distribution maps and reactivity descriptors for 1 and 2 were also determined. The calculated nuclear magnetic resonance spectra of the targets 1 and 2 were well correlated with the experimental data.

Crystal Structure, Vibrational, Spectroscopic and Thermochemical Properties of Double Sulfate Crystalline Hydrate [CsEu(H2O)3(SO4)2]·H2O and Its Thermal Dehydration Product CsEu(SO4)2

Crystalline hydrate of double cesium europium sulfate [CsEu(H2O)3(SO4)2]·H2O was synthesized by the crystallization from an aqueous solution containing equimolar amounts of 1Cs+:1Eu3+:2SO42− ions. Anhydrous salt CsEu(SO4)2 was formed as a result of the thermal dehydration of the crystallohydrate. The unusual effects observed during the thermal dehydration were attributed to the specific coordination of water molecules in the [CsEu(H2O)3(SO4)2]·H2O structure. The crystal structure of [CsEu(H2O)3(SO4)2]·H2O was determined by a single crystal X-ray diffraction analysis, and the crystal structure of CsEu(SO4)2 was obtained by the Rietveld method. [CsEu(H2O)3(SO4)2]·H2O crystallizes in the monoclinic system, space group P21/c (a = 6.5574(1) Å, b = 19.0733(3) Å, c = 8.8364(2) Å, β = 93.931(1)°, V = 1102.58(3) Å3). The anhydrous sulfate CsEu(SO4)2 formed as a result of the thermal destruction crystallizes in the monoclinic system, space group C2/c (a = 14.327(1) Å, b = 5.3838(4) Å, c = 9.5104(6) Å, β = 101.979(3) °, V = 717.58(9) Å3). The vibration properties of the compounds are fully consistent with the structural models and are mainly determined by the deformation of non-rigid structural elements, such as H2O and SO42−. As shown by the diffused reflection spectra measurements and DFT calculations, the structural transformation from [CsEu(H2O)3(SO4)2]·H2O to CsEu(SO4)2 induced a significant band gap reduction. A noticeable difference of the luminescence spectra between cesium europium sulfate and cesium europium sulfate hydrate is detected and explained by the variation of the extent of local symmetry violation at the crystallographic sites occupied by Eu3+ ions, namely, by the increase in inversion asymmetry in [CsEu(H2O)3(SO4)2]·H2O and the increase in mirror asymmetry in CsEu(SO4)2. The chemical shift of the 5D0 energy level in cesium europium sulfate hydrate, with respect to cesium europium sulfate, is associated with the presence of H2O molecules in the vicinity of Eu3+ ion.

Characterization of New Inorganic- Organic Hybrid Compounds: (C6H10N2).Cl2 (I), [C6H10N2]2ZnCl4 (II): Crystal Structure, Hirschfield Surface, IR and NMR spectroscopy Analysis.

Two new organic-inorganic hybrid materials, (C6H10N2).Cl2 (I) and [C6H10N2]2ZnCl4 (II), have been synthesized by hydrothermal method and characterized by single-crystal X-ray diffraction and XRD pattern investigations. These two compounds are crystallized in the monoclinic system; C2/c space group. In the both structures, the anionic-cationic entities are interconnected by hydrogen bonding contacts and p-p Interaction forming three-dimensional networks. Intermolecular interactions were investigated by Hirshfeld surfaces and the contacts of the four different chloride atoms in (II) were compared. The vibrational absorption bands were identified by infrared spectroscopy. These compounds were also investigated by solid state 13C NMR spectroscopy.

Stable Organic-Inorganic Hybrid Bismuth-Halide Monocrystalline Compounds With Adjustable Optoelectronic Properties

Two kinds of novel organic-inorganic bismuth-halide hybrid monocrystalline compounds (C6H5CH2NH3)2BiCl5 and (C6H5CH2NH3)BiI4 were synthesized and characterized. The crystal structure, intermolecular interaction, morphology, chemical groups and bonds, optical and thermal stability of the samples were systematically investigated through single crystal X-ray diffraction, Hirshfeld surface analysis, SEM, FTIR, TG and UV-vis diffuse reflectance spectra. The results indicated that (C6H5CH2NH3)2BiCl5 and (C6H5CH2NH3)BiI4 crystals displayed a monoclinic system with the space group P21/c and P21/n at room temperature, respectively. These materials showed strong absorption in the ultraviolet and visible light regions, resulting in very low Eg, which could be continuously adjustable from 1.67 eV to 3.21 eV by changing the halogen ratio. In addition, these hybrid materials also exhibited good thermal stability. The decomposition temperature of (C6H5CH2NH3)2BiCl5 and (C6H5CH2NH3)BiI4 were 260℃ and 300℃ respectively. Therefore, these organic-inorganic bismuth-halide hybrid compounds have excellent development potential in the field of solar cell research.

Synthesis of Zirconia Micro-Nanoflakes with Highly Exposed (001) Facets and Their Crystal Growth

This study reports a novel preparation method of zirconia micro-nanoflakes with high (001) facets that is generated through a hydrolysis reaction of the fluozirconic acid (H2ZrF6). Zirconia micro-nanoflakes synthesized at varied conditions were analyzed by the SEM, EDS, μ-XRD, and Raman spectroscopy to characterize the morphology and probe into the crystal growth mechanism. The synthesized zirconia crystals in the form of elliptical micro-nanoflakes or irregular nanoflakes generally display the highly exposed (001) facets with a thickness of 1–100 nm and a length of 0.1–2.0 μm. As the temperature and initial solution concentration increased, the particle sizes of the synthesized zirconia micro-nanoflakes became more uniform and the thicknesses of the (001) facets became larger, suggesting that the synthesized zirconia crystals grow along the (001) facets and mostly along the c-axis direction. This is confirmed by the data from the μ-XRD patterns. The results also demonstrate that an oriented attachment-based growth occurring in a fluorine-rich solution environment was involved in the aggregation and coarsening of zirconia micro-nanoflakes. Meanwhile, synthesized zirconia micro-nanoflakes also evolved from a mixture of monoclinic and tetragonal systems to a pure monoclinic system (i.e., baddeleyite) with the temperature increasing, suggesting a key role of temperature regarding zirconia’s growth.

Thiourea Derivatives, Simple in Structure but Efficient Enzyme Inhibitors and Mercury Sensors

In this study six unsymmetrical thiourea derivatives, 1-isobutyl-3-cyclohexylthiourea (1), 1-tert-butyl-3-cyclohexylthiourea (2), 1-(3-chlorophenyl)-3-cyclohexylthiourea (3), 1-(1,1-dibutyl)-3-phenylthiourea (4), 1-(2-chlorophenyl)-3-phenylthiourea (5) and 1-(4-chlorophenyl)-3-phenylthiourea (6) were obtained in the laboratory under aerobic conditions. Compounds 3 and 4 are crystalline and their structure was determined for their single crystal. Compounds 3 is monoclinic system with space group P21/n while compound 4 is trigonal, space group R3:H. Compounds (1–6) were tested for their anti-cholinesterase activity against acetylcholinesterase and butyrylcholinesterase (hereafter abbreviated as, AChE and BChE, respectively). Potentials (all compounds) as sensing probes for determination of deadly toxic metal (mercury) using spectrofluorimetric technique were also investigated. Compound 3 exhibited better enzyme inhibition IC50 values of 50, and 60 µg/mL against AChE and BChE with docking score of −10.01, and −8.04 kJ/mol, respectively. The compound also showed moderate sensitivity during fluorescence studies.