Growth, spectral and thermal characterization of vanillin semicarbazone (VNSC) single crystals

Vanillin semicarbazone (VNSC) has been synthesized from 4-hydroxy 3-methoxy benzaldehyde and semicarbazide hydrochloride using sodium acetate as catalyst. Good quality single crystals of VNSC were successfully grown by slow evaporation method at room temperature using DMF as solvent. The grown crystals have been characterized using melting point, elemental analysis, FT-IR, UV–Visible, ¹H NMR, ¹³C NMR, and X-Ray diffraction analysis. The compound crystallizes into an orthorhombic Pca21 space group. Intermolecular hydrogen bonding interactions facilitate unit cell packing in the crystal lattice. The UV–Visible spectrum confirmed the transparency of the compound between the wavelengths 420 and 1,200 nm, which is characteristic to property of an NLO material. The thermal decomposition of the compound under static air atmosphere was investigated by simultaneous TG/DTG at a heating rate of 10 °C/min.     

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.     

Growth, spectral, and thermal characterization of semicarbazone of p-hydroxy acetophenone (SPHA)

A new organic nonlinear optical material semicarbazone of p-hydroxy acetophenone (SPHA) was synthesized. Good quality single crystal of SPHA was successfully grown by slow evaporation method at room temperature. The crystal system was identified and lattice dimensions were measured from the single crystal X-ray diffraction (XRD) analysis. The various planes of reflection were identified from the powder XRD pattern. The presence of functional groups was qualitatively found by Fourier transform infrared (FTIR) spectral analysis. The proton and carbon nuclear magnetic resonance (¹HNMR and ¹³CNMR) spectral studies confirmed the presence of hydrogen and carbon bonded network in the grown crystal. The UV?CVisible absorption spectrum was recorded to study the optical transmittance in the range from 200 to 800?nm. The thermal stability of compound was determined by thermogravimetric and differential thermal analysis (TG-DTA) traces. The existence of second harmonic generation (SHG) signal was observed using Nd:YAG laser with fundamental wavelength of 1064?nm.     

Synthesis and characterization of a new organic nonlinear optical crystal: l-Phenylalaninium maleate

l-Phenylalaninium maleate (abbreviated as LPM) chemical formula C₉H₁₂NO₂⁺·C₄H₃O₄⁻, a new organic nonlinear optical crystal was grown by slow evaporation technique. Transparent needle shaped crystal of dimensions 7 mm × 1 mm × 0.5 mm was obtained. Single crystals of LPM have been subjected to X-ray diffraction analysis to estimate the lattice parameters and the space group. The powder X-ray diffractogram of the crystal has been recorded and the reflections from various planes are identified. The XRD studies confirm the crystalline nature. The qualitative analysis on the crystal has been carried out using Fourier transform infrared (FTIR) and Fourier transform Raman (FTRaman) spectral measurements. The presence of hydrogen and carbon in the grown crystal was confirmed by using proton and carbon nuclear magnetic resonance (NMR) spectral analyses. Optical behaviour of the crystal was investigated using UV–vis spectroscopy. The thermal stability of the crystal was analysed with the aid of thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). The nonlinear optical (NLO) property of the crystal was tested by Nd:YAG laser source.     

Growth and characterization of semiorganic NLO crystal of l-glutamic acid hydrochlorobromide (LGHCB)

Single crystals of nonlinear optical material l-glutamic acid hydrochlorobromide (LGHCB) were grown by slow evaporation technique from its aqueous solution. Optically good quality crystals of dimension 20 × 10 × 2 mm³ were obtained. The lattice parameters for the grown crystals were determined using single crystal X-ray diffraction study. The LGHCB crystal belongs to non-centrosymmetric P2₁2₁2₁ space group. The crystal structure was resolved by direct method and refined by full matrix least-square method using SHELXL-97. Using the powder X-ray diffraction study, the crystallinity of the grown crystal was confirmed and the diffraction peaks are indexed. From Fourier transform infrared spectroscopy study, the various functional groups present in LGHCB crystal were elucidated. The UV–Vis-NIR absorption spectrum was recorded in the range of 200–2,000 nm, and the lower cut off wavelength is ~235 nm. Optical band gap of the grown crystal was found to be 5.22 eV. Thermal properties of LGHCB crystal were studied by thermogravimetric analysis and derivative thermogravimetric analysis. The second harmonic generation efficiency of LGHCB crystal was confirmed by Kurtz’s powder technique.     

Growth,spectral, and thermal characterization of the NLO crystal: semicarbazone of <Emphasis Type="SmallCaps">dl</Emphasis>-camphor (SDLC)

Semicarbazone of dl-camphor (SdlC) crystals were grown using methanol as a solvent by slow evaporation solution growth technique at room temperature. Formation of the product and the presence of various functional groups present in the grown crystal have been identified using FTIR spectra. Single crystal XRD study was conducted to obtain the crystal structure and lattice parameters. The grown crystal was subjected to ¹HNMR and ¹³CNMR spectral studies and TG-DTA in order to confirm its structure, purity, and stability, respectively. The optical transparency of the crystal was tested using UV–Vis–NIR spectroscopy. The nonlinear optical (NLO) property of the grown crystal was confirmed from the second harmonic generation (SHG) by Kurtz–Perry powder test.     

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.     

Growth, optical, thermal, and conductivity behavior of nonlinear optical single crystals of CdHg(SCN)4(CH3OC2H5O)

In this study, organometallic nonlinear optical single crystal of Cadmium mercury thiocyanate glycol monomethyl ether was grown by slow evaporation technique at room temperature. The grown crystal was confirmed by single crystal XRD and FT-IR analysis. Optical and thermal properties of the sample were investigated by UV–Vis–NIR, TG–DTA and DSC technique. Using Tauc’s relation, the band gap of the crystal was estimated as 3.99 eV. The thermal studies confirm that the CMTG is thermally stable up to 105 °C. Photoluminescence and ac & dc conductivity measurements of the sample were also carried out and reported for the first time. The PL analysis confirms the suitability of the material for application in the blue–green region. The temperature dependences of ac & dc conductivities of CMTG were investigated, and the activation energies were found to be 0.098 and 0.045 eV, respectively. The SHG efficiency measurement confirms that the NLO efficiency of CMTG is nearly three times more efficient than urea.     

Synthesis, growth, and characterization of iminodiacetic acid monohydrochloride

The title compound of iminodiacetic acid hydrochloride (IDAAMHCL) has been successfully synthesized by adopting conventional chemical reaction and the single crystals have been grown by solvent evaporation method at room temperature and studied its various properties and reported for the first time. The lattice dimension and the crystal structure were identified from the powder X-ray diffraction analysis. The crystalline perfection assessed by high resolution X-ray diffraction technique shows that the specimen is free from structural grain boundaries. The presence of functional groups and the protons in IDAAMHCl was confirmed by Fourier transform infra-red and NMR (¹H and ¹³C) spectroscopic techniques. The presence of carbon, hydrogen, and nitrogen was confirmed by elemental analysis. The optical behavior of IDAAMHCl was assessed by UV-visible spectroscopy and it is found that there is no absorption in the entire visible region of the spectrum. The Z scan measurements at 532 nm with 5 ns laser pulses show that IDAAMHCL is a very good candidate for optical limiting applications.     

Growth, structure, and characterization of tris(thiourea)silver(I) nitrate

Single crystals of tris(thiourea)silver(I) nitrate have been grown by slow evaporation solution growth technique from an aqueous solution at 25 °C. The single crystal X-ray diffraction study reveals that the crystal belongs to tetragonal system and cell parameters are a = b = 14.2790(4) Å, c = 24.8900(7) Å, and V = 5074.8(2) Å³. The various functional groups present in the molecule are confirmed by Fourier transformed infrared spectroscopy (FT-IR). The structure and the crystallinity of the materials were further confirmed by powder X-ray diffraction analysis. Thermogravimetric and differential thermal analysis reveal the purity of the sample and no decomposition is observed up to the melting point. The crystal is further characterized by UV–Vis and Vickers microhardness analysis.     

Synthesis, growth, thermal, optical, mechanical and dielectric studies of N-succinopyridine

Organic nonlinear optical (NLO) material, N-succinopyridine (NSP), was synthesised and bulk single crystals were grown from aqueous solution using isothermal solvent evaporation technique. The stoichiometric form of NSP has been confirmed by carbon–hydrogen–nitrogen analysis. NSP crystallizes in orthorhombic system with non-centrosymmetric space group P2₁2₁2₁ and unit cell dimensions a = 7.721(2) Å, b = 7.762(3) Å, c = 14.951(3) Å. The thermal stability, thermal decomposition and specific heat capacity of NSP have been investigated by thermogravimetric/differential thermal analysis, differential scanning calorimetric (DSC) analysis and modulated DSC analysis. A wide transparency window, 294–1,100 nm, useful for optoelectronic applications is indicated by UV–Vis–NIR studies. The NLO second harmonic generation efficiency analysis using Nd:YAG laser (1,064 nm) revealed that the SHG efficiency of NSP is about 1.2 times higher than that of standard potassium dihydrogen phosphate powder of comparable size and more importantly that it is phase-matchable. The room temperature mechanical behaviours of NSP have been tested using Vicker’s microhardness tester and the results were analysed through classical Mayer’s law. The dielectric behaviours such as dielectric constant, dielectric loss and ac conductivity of NSP single crystal have also been investigated as a function of frequency (20 Hz–1 MHz) and temperature (308–358 K).     

Synthesis, growth, structure and characterization of a new semiorganic crystal

A new semiorganic single crystal, tris(allylthiourea)silver(I) nitrate was grown from an aqueous solution containing silver(I) nitrate and allylthiourea by slow evaporation solution growth technique at room temperature. The crystal belongs to trigonal system with centrosymmetric space group R3 and the cell parameters are, a = 12.5090(4) Å, b = 12.5090(4) Å, c = 21.7130(8) Å, V = 3348.89 Å³, and Z = 6. The various functional groups present in the molecule are confirmed by Fourier transformed infrared spectroscopy. High transmittance is observed in the visible region and band-gap energy is calculated by Kubelka–Munk algorithm. The structure and the crystallinity of the materials were further confirmed using powder X-ray diffraction analysis. Microhardness studies were also carried out to elucidate the mechanical behavior. Thermogravimetric and differential thermal analysis reveal the purity of the sample and no decomposition is observed up to the melting point.     

Synthesis, growth, structure, and characterization of a novel semiorganic crystal

Single crystals of (chloro)tris(thiourea-κS)cadmium(II) picrate have been grown by slow evaporation of a mixed solvent system water–acetone containing thiourea, cadmium chloride, and picric acid. The yellow crystals belong to triclinic system with centrosymmetric space group P-1 and the corresponding lattice parameters are a = 7.4632(3) ?, b = 7.9567(3) ?, c = 17.4885(7) ?, α = 98.990(2)°, β = 100.137(2)°, γ = 95.275(2)°, and Z = 2. The vibrational patterns of the as-grown crystals are analyzed by FT-IR and FT-Raman spectral analyses. The optical absorption study was performed to analyze the optical transparency of CTTCP and the crystals were transparent in the visible region and have a lower optical cutoff at ~507 nm with band gap energy of 2.47 eV. TG–DTA thermal analysis shows that the crystal is stable up to ~208 °C and has a good chemical stability.     

Theoretical investigation of a high density cage compound 1,3,5,7,9,11-hexanitrotetradecahydro-1H-1,3,4,5,7,7b,9,11,12a,12b1,12b2,13-dodecaaza-4,8,12-(epimethanetriyl)cyclohepta[l]cyclopenta[def] phenanthrene

The B3LYP/6-31G** method was used to investigate IR and Raman spectra, heat of formation, and thermodynamic properties of a new designed polynitro cage compound 1,3,5,7,9,11-hexanitrotetradecahydro-1H-1,3,4,5,7,7b,9,11,12a,12b¹,12b²,13-dodecaaza-4,8,12-(epimethanetriyl)cyclohepta[l]cyclopenta[def]phenanthrene. The detonation and pressure were evaluated using the Kamlet–Jacobs equations based on the theoretical density and HOFs. The bond dissociation energies and bond orders for the weakest bonds were analyzed to investigate the thermal stability of the title compound. The results show that N₈–NO₂ bond is predicted to be the trigger bond during pyrolysis. There exists an essentially linear relationship between the WBIs of N–NO₂ bonds and the charges – $ Q_{{{\text{NO}}_{ 2} }} $ on the nitro groups. The crystal structure obtained by molecular mechanics belongs to the P2₁ space group, with lattice parameters Z = 2, a = 11.4658 Å, b = 15.2442 Å, c = 10.2451 Å, ρ = 2.07 g cm^?3. The designed compound has high thermal stability and good detonation properties and is a promising high-energy density compound.     

Synthesis,thermal decomposition and dielectric behavior of bis(thiourea)silver(I)nitrate

New semi-organic bis(thiourea)silver(I)nitrate (TuAgN) single crystals have been grown from slow evaporation solution growth technique. Single crystal X-ray diffraction study reveals that the crystal belongs to orthorhombic system with the non-centrosymmetric space group C2221 and the calculated cell parameters are a = 33.3455 (6) Å, b = 45.2957 (7) Å, c = 20.3209 (5) Å, α = β = γ = 90°, and V = 30692.8 (10) Å ³. The thermal stability and decomposition behavior of TuAgN compound have been studied by thermogravimetric analysis at three different heating rates 5, 10, and 15 °C min^?1. The effective activation energy (E _a) and pre-exponential factor (ln A) of thermal decomposition of thiourea from TuAgN compound at three different heating rates are estimated by model free methods: Arrhenius, Flynn–Wall, Kissinger, and Kim–Park. The calculated effective activation energies were found to vary with the fraction (α) reacted. The compensation effect between the (ln A) and (E _a) has also been studied. Dielectric properties of TuAgN crystal have been studied in a wide range of frequencies and temperatures. AC conductivity has also been carried out.     

Synthesis,growth and characterization of hydrogen bonding organic complex for SHG conversion: 3-hydroxyanilinium-2,5-dimethylbenzenesulphonate single crystal

The new hydrogen bonding single crystal of 3-hydroxyanilinium-2,5-dimethylbenzenesulphonate (3HADB) complex has been synthesized and grown by slow evaporation solution growth technique. The grown crystal was confirmed by single crystal X-ray diffraction, Fourier Transform Infrared (FT-IR) and proton Nuclear Magnetic Resonance (¹HNMR) spectral studies. Single crystal X-ray diffraction study shows that 3HADB crystallizes in the orthorhombic crystal system with noncentrosymmetric Pna2₁ space group. The title compound was characterized by UV–Vis–NIR absorption and TG/DTA thermal analysis studies. The second harmonic generation efficiency of powdered 3HADB was determined by Kurtz and Perry method.     

Crystal growth, spectral, optical, and thermal characterization of glycyl-l-alanine hydrochloride (GLAH) single crystal

A new semi-organic nonlinear optical material glycyl-l-alanine hydrochloride (GLAH) was grown successfully by slow evaporation solution growth method. The solubility of GLAH was estimated for a wide range of temperatures. Large size single crystal of size 15?×?9?×?6?mm³ was grown at room temperature. The grown crystal was subjected to single crystal X-ray diffraction study which confirms that the grown crystal is monoclinic in nature with the space group P2₁. The molecular weight of the title compound was estimated by mass spectrometry. Functional groups and the modes of vibrations were identified by FT-IR spectral analysis. The UV?Cvisible spectral study reveals that the percentage of optical transmission of the sample is very high in the entire visible and UV regions. The second harmonic generation of the crystal was confirmed by the Kurtz and Perry technique. The hardness of the sample was tested by microhardness test which shows that the grown crystal belongs to the soft category of materials. The thermal stability of the compound was studied by TG?CDTA analyses which indicate that the crystal is thermally stable up to 248.6?°C.     

Growth and characterization of a new metal-organic nonlinear optical bis (thiourea) cadmium zinc chloride single crystals

A new semiorganic nonlinear optical bis (thiourea) cadmium zinc chloride (BTCZC) crystal has been synthesized. BTCZC single crystals were grown from aqueous solution by slow evaporation technique. The solubility of BTCZC has been determined for various temperatures. Single crystal X-ray diffraction (XRD) study has been carried out to identify the lattice parameters. Fourier transform infrared (FTIR) studies confirm the various functional groups present in the grown crystal. The transmission and absorption spectra of this crystal show that the lower cut off wavelength lies at 260nm. The thermal analyses confirmed that the crystal is stable upto 201 degrees C. The nonlinear optical (NLO) property of the grown crystal has been confirmed by Kurtz-powder second harmonic generation (SHG) test.     

Investigation on structural,spectral, and thermal properties of l-histidinium glutarate monohydrate (LHG)

l-histidinium glutarate monohydrate, an organic nonlinear optical crystal has been successfully grown from deionized water by slow solvent evaporation method at room temperature. Crystal structure and its lattice parameters were identified by single-crystal X-ray diffraction technique. Crystalline perfection of the grown crystal was studied by high-resolution X-ray diffraction rocking curve measurements by employing a multicrystal X-ray diffractometer. FT-IR and FT-Raman spectral studies were employed to identify the presence of various functional groups and mode of vibrations in the crystal. Thermal behavior of the crystal was studied by TG–DTA, TG–DTG, and DSC analyses. Optical absorption of the crystal in the wavelength region 200–1,000 nm was studied by UV–Vis–NIR spectral analysis. Kurtz and Perry powder technique was employed to find the second harmonic generation efficiency of the crystal.     

Synthesis,spectral, and thermal properties,and crystal structure of cobalt (III) complex derived from Imazameth

A novel metal–organic coordination compound [Co(Imazameth)₃]·0.5DMF·4H₂O (where Imazameth = (±)-2-(4,5-dihydro-4-methyl-4-(1-methylethyl)-5-oxo-1H- imidazol-2-yl)-5-methyl-3-pyridinecarboxylic acid; DMF = N,N-dimethylformamide) has been prepared and characterized by spectral method (IR), elemental analysis, thermal gravimetric analysis (TGA), fluorescence properties, and single crystal X-ray diffraction techniques. It crystallizes in the trigonal system, space group R-3 and the asymmetric unit contains four water molecules. The four lattice water molecules and their symmetric equivalent form a slight distorted cubical water cluster through hydrogen bonds. The O···O bonds of the water cluster are in the range of (2.80(7)–2.99(2) Å), and O···O···O angles are in the range of (82.54°–101.38°). In the cubical water clusters, the six O(5) atoms of each cube are connected to six O(1) atoms of the six molecules (O(1)···O(5) = 2.77(1) Å) by hydrogen bonding, respectively. The Co atom is six-coordinated by six N atoms in distorted octahedron coordination geometry. Intramolecular N–H···O and intermolecular O–H···O hydrogen bonds result in the formation of a supermolecular crystal, in which they seem to be effective in the stabilization of the structure. The complex displays strong fluorescence property and good thermal stability.