Structural, thermal and optical characterization of an organic NLO material--benzaldehyde thiosemicarbazone monohydrate single crystals

Single crystals of the organic NLO material, benzaldehyde thiosemicarbazone (BTSC) monohydrate, were grown by slow evaporation method. Solubility of BTSC monohydrate was determined in ethanol at different temperatures. The grown crystals were characterized by single crystal X-ray diffraction analysis to determine the cell parameters and by FT-IR technique to study the presence of the functional groups. Thermogravimetric and differential thermal analyses reveal the thermal stability of the crystal. UV-vis-NIR spectrum shows excellent transmission in the region of 200-1100 nm. Theoretical calculations were carried out to determine the linear optical constants such as extinction coefficient and refractive index. Further the optical nonlinearities of BTSC have been investigated by Z-scan technique with He-Ne laser radiation of wavelength 632.8 nm. Mechanical properties of the grown crystal were studied using Vickers microhardness tester. Second harmonic generation efficiency of the powdered BTSC monohydrate was tested using Nd:YAG laser and it is found to be ～5.3 times that of potassium dihydrogen orthophosphate.     

Vibrational spectroscopic analysis of cytosine monohydrate and its copper(II) complex

Single crystals of cytosine monohydrate and its copper(II) complex were grown by slow evaporation in an aqueous solution at room temperature. The solubility studies were carried out at different temperatures in deionized water. Cytosine monohydrate and the copper(II) complex of cytosine were characterized by recording IR, Raman and UV spectra. The various vibrational modes of the crystals have been classified using factor group and site group analysis. Vibrational assignments were proposed for both the systems based on the spectral investigations.     

Spectral, optical, and thermal studies of pure and Zn(II)-doped l-histidine hydrochloride monohydrate (LHHC) crystals

The influence of doping the transition metal Zn(II) on the growth, spectral, optical, and thermal properties of l-histidine hydrochloride monohydrate (LHHC) crystals grown by slow solvent evaporation method has been investigated. Structural characterizations of the grown crystals were carried out by single crystal X-ray diffraction analysis and it shows slight structural changes as a result of doping. The FT-IR spectral study reveals the presence of various functional groups and confirms the slight distortion of the structure of the crystals due to doping. The energy dispersive X-ray analysis reveals the incorporation of Zn(II) in the crystalline matrix of LHHC crystal. The UV?CVis spectral study was carried out to analyze the optical transmittance of the grown crystals and found that the transmittance is very high in the visible and UV regions for both pure and doped crystals. The second harmonic generation (SHG) for the grown crystals was confirmed by Nd:YAG laser. The scanning electron microscopy reveals the presence of defect centers and crystal voids. The thermal stability and purity of the grown crystals were analyzed by thermogravimetry, differential thermal analysis, and differential scanning calorimetry techniques.     

Synthesis,crystal growth,structural, spectral,optical, thermal and dielectric studies of a new nonlinear optical material: 4-Hydroxy-l-proline-l-tartaric acid (1:1)

Single crystals of a new organic material, 4-hydroxy-l-proline-l-tartaric acid (HPTA) adduct, were grown by slow evaporation of an aqueous solution containing equimolar concentrations of 4-hydroxy-l-proline and l-tartaric acid at room temperature. Formation of new crystal has been confirmed by single crystal X-ray diffraction and NMR spectroscopic techniques. The single crystal XRD analysis shows that a molecule of 4-hydroxy-l-proline and a molecule of free l-tartaric acid both of which are interlinked to each other by two types of H-bonding interactions, namely O(6)–H(6)⋯O(2) and N(1)–H(1B)⋯O(10). The title compound (HPTA) crystallizes in monoclinic crystal system with non-centrosymmetric space group P2₁. The suitability of the crystal for optical applications was studied by UV–Vis–NIR spectroscopy. Fourier transform infrared (FT-IR) spectral analysis was used to confirm the presence of various functional groups in the grown crystals. The thermal stability of the compound was investigated by thermogravimetric and differential thermal analyses. The dielectric constant and dielectric loss of the crystal were studied as a function of frequency and temperature. The fluorescence spectral analysis of the title crystal shows an indigo emission. The second order nonlinear optical (NLO) property of the crystal was confirmed by the modified Kurtz–Perry powder second harmonic generation (SHG) test.     

Crystal growth, structural, optical, spectral and thermal studies of tris(L-phenylalanine)L-phenylalaninium nitrate: a new organic nonlinear optical material

Tris(L-phenylalanine)L-phenylalaninium nitrate, C(9)H(12)NO(2)(+)·NO(3)(-)·3C(9)H(11)NO(2) (TPLPN), a new organic nonlinear optical material was grown from aqueous solution by slow evaporation solution growth at room temperature. The grown crystals were subjected to powder X-ray diffraction and single crystal X-ray diffraction studies to confirm the crystalline nature and crystal structure. The modes of vibration of different molecular groups present in TPLPN have been identified by FTIR spectral analysis. The presence of hydrogen and carbon in the grown crystal were confirmed by using proton and carbon nuclear magnetic resonance (NMR) spectral analyses. The optical transmission spectral study establishes good transmitting ability of the crystal in the entire visible region. The thermogravimetric (TG) and differential thermal analyses (DTA) were carried out to understand the thermal stability of the sample. The nonlinear optical property of the compound observed using Kurtz powder second harmonic generation test assets the suitability of the grown material for the frequency conversion of laser radiation of Nd:YAG.     

Thermal FT-IR microspectroscopy for rapid detection of solid-state ion-exchange reaction between metoclopramide HCl monohydrate and potassium bromide

The combination of Fourier transform infrared (FT-IR) microspectroscopy with a thermal analyzer was applied to quickly investigate the solid-state ion-exchange reaction of metoclopramide HCl monohydrate (MCP H(2)O) by clipping MCP H(2)O powder between two KBr or KCl pellets. The physical and ground mixtures of MCP H(2)O or 150 °C-preheated MCP powder and KBr or KCl powders with a weight ratio of 1 : 100 were also prepared and determined by FT-IR microspectroscopy. The samples of MCP H(2)O or 150 °C-preheated MCP were identified by using differential scanning calorimetry (DSC) and thermogravimetric (TG) analysis. The results of present study indicate that the ion-exchange reaction was easily induced between MCP H(2)O and KBr by grinding and heating processes. The possible mechanism of ion-exchange reaction may take place between the HCl salt of MCP H(2)O and a KBr matrix by grinding or heating to yield a mixture of HCl and HBr salts of the MCP sample in the presence of hydrated water. The crystal hydrate played an important role to improve this ion-exchange reaction between MCP H(2)O and KBr. However, no ion-exchange reaction occurred between MCP H(2)O and KCl or between 150 °C-preheated MCP and KBr. The solid-state ion-exchange reaction was more easily determined by this novel thermal FT-IR microspectroscopy than other conventional methods.     

Synthesis of double ammonium’calcium pyrophosphate monohydrate Ca(NH4)2P2O7•H2O as the p recursor of biocompatible phases of calcium phosphate ceramics

Russian Chemical Bulletin - Double calcium’ammonium pyrophosphate monohydrate Ca(NH4)2P2O7?H2O was synthesized as a result of the interaction of calcium carbonate, an aqueous solution...     

Synthesis, structural, thermal and optical studies of 1-ethyl-2,6-dimethyl-4-hydroxy pyridinium halides

1-Ethyl-2,6-dimethyl-4-hydroxy pyridinium chloride dihydrate and bromide dihydrate salts have been synthesized and their single crystals were grown by the slow evaporation of aqueous solution at 30 degrees C. The grown crystals were characterized by elemental analysis, FT-NMR and FT-IR techniques to confirm the formation of the expected compound. Optical transmittance window in aqueous solution was found to be 275-1100 nm by UV-vis-NIR technique. Thermogravimetric and differential thermal analyses reveal thermal stability and the presence of two water molecules in the crystal lattices. The crystal structure of chloride salt was also determined by X-ray diffraction method.     

5-氨基间苯二甲酸钠和5-羟基间苯二甲酸钠的热力学性质

在水溶液中合成了5-氨基间苯二甲酸钠(1)和5-羟基间苯二甲酸钠(2)固态样品,元素分析和TG-DTG确定其组成符合C8H5O4NNa2·H2O(1)和C8H4O5Na2·H2O(2).用精密自动绝热热量计测定了它们在78～400K温区的低温热容,将实验值用最小二乘法拟合,得到热容随温度变化的多项式方程,用此方程进行数值积分,得到该温区内每隔5K的舒平热容值和各种热力学函数值.用RD496-2000型微热量计测定了样品在298.15K时的标准摩尔溶解焓分别为ΔsolHmθ(1,s)=-44.552±0.164kJmol-1和θΔsolHm(2,s)=-36.055±0.154kJmol-1,计算了其水合阴离子标准摩尔生成焓分别为θΔfHm(C8H5O4N2-,aq)=-684.56±1.67kJmol-1和ΔfHmθ(C8H4O52-,aq)=-1263.43±2.13kJmol-1.用RBC-II型精密转动弹热量计测定了样品的恒容燃烧热分别为ΔcU(1,s)=-13382.14±5.28Jg-1和ΔcU(2,s)=-10339.15±4.15Jg-1,计算了它们的标准摩尔燃烧焓和标准摩尔生成焓分别为ΔcHmθ(1,s)=-3252.90±1.28kJmol-1和θΔcHm(2,s)=-2522.64±1.01kJmol-1,ΔfHmθ(1,s)=-1406.46±1.66kJmol-1,θΔfHm(2,s)=-1993.79±1.46kJmol-1.     

Synthesis of CdSnO(3).3H(2)O nanocubes via ion exchange and their thermal decompositions to cadmium stannate

Uniform crystalline CdSnO3.3H2O nanocubes with a 28-35 nm edge length have been obtained via the ion-exchange reaction of Na2Sn(OH)6 in a CdSO4 aqueous solution, assisted by ultrasonic treatment. Precursor Na2Sn(OH)6 crystals were prepared via hydrothermal treatment in an ethanol/water solution. The formation of CdSnO3.3H2O nanocubes resulted from the strain during the ion-exchange process. The influences of reaction conditions, such as ion-exchange (ultrasonic treatment) duration, solvent constitutes, surfactant, and pH on the formation of CdSnO3.3H2O crystals were described. Crystalline CdSnO3 and Cd2SnO4 have been obtained by thermal treatment at 300 and 500 degrees C, respectively, for 5 h under an inert-gas protecting condition using CdSnO3.3H2O nanocubes as the precursor. The cube shape of CdSnO3.3H2O was sustained after thermal decomposition to CdSnO3.     

Synthesis, growth and characterization of a new nonlinear optical material: 4-phenylpyridinium hydrogen squarate (4PHS)

A novel organic non-linear optical organic single crystal of 4-phenylpyridinium hydrogen squarate (4PHS) has been synthesized and successfully grown from aqueous solutions by slow evaporation solution growth method. In the present investigation the title compound has been synthesized by taking equimolar quantity of 4-phenylpyridine and squaric acid and mixed thoroughly using double distilled water as the solvent. The prepared concentrated solution was placed in an undisturbed condition, and then the solution was periodically inspected. The good quality single crystals have been harvested in a time span of 3 weeks. Then the grown crystal was characterized as single crystal XRD, differential thermal analysis, thermogravimetric analysis, FTIR, UV-vis-NIR, SHG, (1)H NMR and (13)C NMR analyses, respectively. The observed results from the characterization analyses show its suitability for NLO applications when compared with some of the existing organic crystals. The relative second harmonic generation of this grown crystal was found to be five times higher than that of KDP crystal. The UV cut-off wavelength and decomposition temperature of this grown crystal were also comparatively better. (1)H NMR and (13)C NMR spectroscopic studies were employed to elucidate the structure of the grown specimen.     

三氨基胍三硝基间苯二酚盐的制备、晶体结构及热分解

利用三氨基胍和斯蒂芬酸制备得到了三氨基胍三硝基间苯二酚盐, 培养出了可用于X射线衍射的单晶. 利用元素分析、红外光谱、差示扫描量热法(DSC)、热重-微分热重法(TG-DTG)和X射线单晶衍射等方法对标题化合物的组成和结构进行了表征. 晶体属于三斜晶系, 空间群为P-1, 晶胞参数a＝0.75554(15) nm, b＝0.90816(18) nm, c＝1.0264(2) nm, α＝101.61(3)°, β＝91.96(3)°, γ＝107.74(3)°, V＝0.6536(2) nm3; Dc＝1.775 g/cm3; Z＝2; F(000)＝360, μ＝0.160 mm－1, R1＝0.0479, ωR2＝0.0998. 晶体结构分析结果表明, 该化合物分子式为C7N9O7H11, 是由[C(N2H3)3]＋和(C6N3O8H2)－结合成的离子化合物, 分子中含有大量的氢键, 结构较为稳定. 热分析结果表明, 在10 K/min的升温速率下, 标题化合物的热分解过程由1个吸热峰和3个放热峰组成, 分解产物大部分为气相产物, 剩余残渣量在1%左右.     

Studies on the growth, spectral, optical, and thermal aspects of a NLO crystal

Nonlinear optical single crystal l-tryptophan hydrogen selenite (LTHS) has been synthesized by slow evaporation solution growth technique from aqueous solution at ambient temperature. The grown nonlinear optical crystals were subjected to single crystal XRD analysis to find the structure parameters. The formation of the product was confirmed from the FTIR and ¹HNMR spectral analysis. The UV–Vis spectral studies showed that the cutoff wavelength for LTHS was less than 400 nm. The thermal behavior of the grown crystals was investigated from thermogravimetry and differential thermal analysis. Its nonlinear optical property has been tested by Kurtz–Perry powder technique using Nd:YAG laser, and the crystal exhibited second harmonic generation property.     

Crystal growth, thermal and optical studies on a semiorganic nonlinear optical material for blue-green laser generation

The semiorganic nonlinear optical material l-histidine bromide (l-HB) has been synthesized in aqueous solution and characterized by FT-IR, FT-Raman and FT-NMR spectroscopic techniques. The single crystals with dimensions 9mm x 4mm x 3mm were grown by slow evaporation techniques. The grown crystals were subjected to single crystal X-ray diffraction to determine the unit cell dimensions. The thermal stability of the grown crystal was analyzed by thermogravimetric (TG), differential thermal (DT) and differential scanning calorimetric (DSC) analyses. The UV-vis transmittance spectrum shows that it has a good optical transmittance in the entire visible region with the lower cutoff wavelength at 220 nm. The SHG conversion efficiency and laser damage threshold were measured using a Nd:YAG laser (1064 nm). The optical birefringence was measured in the visible region as a function of temperature in the range 30-150 degrees C by interference technique.     

Synthesis, X-ray and neutron diffraction characterization, and ionic conduction properties of a new oxothiomolybdate Li3[Mo8S8O8(OH)8[HWO5(H2O)]] x 18H2O

The new oxothiomolybdate anion [Mo8S8O8(OH)8[HWO5(H2O)]]3- (denoted HMo8W3-) has been synthesized in aqueous solution by an acido-basic condensation reaction. Four (Mo(V)2S2O2) building blocks are connected through hydroxo bridges around a central [W(VI)O6] octahedron. X-ray and neutron diffraction studies have been performed on single crystals of the lithium salt Li3[Mo8S8O8(OH)8[HWO5(H2O)]] x 18H2O (Li3HMo8W x 18H2O) in an aqueous grown from HMo8W3- solution of LiCl (1 M). The neutron diffraction experiment enabled us to locate both the protons and the lithium ions. In the structure of Li3HMo8W x 18H20, ring-shaped anions interleaved by a cluster of disordered hydrogen-bonded water molecules stack on top of each other along lithium pillars. The lithium columns are formed by alternating edge-sharing octahedra and tetrahedra, with one lithium site in four being totally vacant. Ionic conductivity measurements on pressed pellets have shown that Li3HMo8W x 18H2O is a good ionic conductor at room temperature (sigma = 10(-5) S cm(-1)), but the ionic conductivity on single crystals is smaller by two orders of magnitude and is isotropic; this suggests the main path of conduction involves surface protons rather than lithium ions of the bulk.     

Crystal growth, structural and spectroscopic analysis of hypoxanthinium chloride monohydrate

Protonated form of hypoxanthinium chloride monohydrate single crystal has been grown from dilute hydrochloric acid. Single crystal X-ray analysis was carried out and the titled crystal belong to the monoclinic P2(1)/c space group. Hypoxanthine is protonated at N(1) with the hypoxanthine cations, linked to chlorine anion via weak bifurcated N-H...Cl hydrogen bonds and interconnected by hydrogen bonding contacts of the type N-H...O. Infrared, Raman and UV spectroscopic tools were applied to characterize hypoxanthinium chloride monohydrate. By applying group theoretical methods the internal and external modes of vibrations of the title crystal have been identified and discussed.     

Growth and characterization of sodium pentaborate [Na(H4B5O10)] single crystals

The bulk single crystals of sodium pentaborate [Na(H4B5O10)] were grown by slow evaporation solution growth technique using deionized water as solvent. The grown crystal was confirmed by single crystal X-ray diffraction studies. The structural perfection of the grown crystals has been analyzed by high resolution X-ray diffraction (HRXRD) studies by recording rocking curve. The photoluminescence (PL), UV-vis spectral studies were performed and the optical bandgap of the material was calculated. The presence of the functional groups was identified by FT-IR measurement. The factor group analysis was done on Na(H4B5O10) to reveal the vibrational optical modes. The thermal and mechanical properties of the grown crystal were studied by TG-DTA and Vickers microhardness tester, respectively. The dielectric behavior of Na(H4B5O10) was investigated with different frequencies and temperatures.     

Diplatinum(ii)-coordinated polyoxotungstate: synthesis, molecular structure, and photocatalytic performance for hydrogen evolution from water under visible-light irradiation

The synthesis and molecular structure of a monomeric diplatinum(ii) complex composed of mono-lacunary α-Keggin polyoxometalate is described. The polyoxometalate, Cs(3)[α-PW(11)O(39){cis-Pt(NH(3))(2)}(2)]·8H(2)O (Cs-1), afforded by a stoichiometric reaction of mono-lacunary Keggin polyoxotungstate with cis-diamminedichloroplatinum(ii) in water, followed by crystallization from water, was obtained as analytically pure, homogeneous, yellow crystals. The compound Cs-1 was characterized by elemental analysis, thermogravimetric/differential thermal analysis (TG/DTA), Fourier transform infrared (FTIR) and UV-visible spectroscopy, solution (1)H and (31)P nuclear magnetic resonance (NMR), and X-ray crystallography. The single-crystal X-ray structure analysis revealed that the two cis-platinum(ii) moieties, [cis-Pt(NH(3))(2)](2+), were coordinated each to two oxygen atoms in a mono-vacant site of [α-PW(11)O(39)](7-) with asymmetric configuration, resulting in an overall C(1) symmetry. Furthermore, hydrogen evolution from an EDTA·2Na (ethylenediamine tetraacetic acid disodium salt) aqueous solution under visible-light irradiation (≥400 nm) was achieved by using polyoxoanion 1 and titanium dioxide.     

Spectroscopic and optical studies on pure and doped single crystals of sulphate-mixed L-arginine phosphate monohydrate--a nonlinear optical crystal

Single crystals of pure and transition metal ions (Cu(2+) and VO(2+))-doped L-arginine sulpho phosphate monohydrate (sulphate-mixed L-arginine phosphate monohydrate, abbreviated as LASP) have been grown by solvent evaporation of the saturated aqueous solution at room temperature and characterized by single-crystal XRD, FT-IR, UV-Vis-NIR and EPR (single-crystal rotation) spectral studies. Kurtz powder technique shows an enhanced second harmonic generation (SHG) efficiency for LASP and its doped analogues than pure LAP. The EPR studies on LASP:VO(2+) reveal that the in-plane sigma-bonding is moderately covalent and the out-of-plane pi-bonding is highly covalent, which could be attributed to the cause of enhanced powder efficiency.     

Thermal degradation and spectroscopic studies of single-crystalline organometallic calcium adipate monohydrate

Journal of Thermal Analysis and Calorimetry - Calcium adipate monohydrate single crystals were grown by single gel diffusion technique using silica gel as a medium of growth. The powder X-ray...