Slow Evaporation Solution Growth Technique Research Articles

Growth, characterization and chemical computations of guanidinium trichloroacetate (GTCA) single crystal – DFT approach

ABSTRACT. Nonlinear optical (NLO) active guanidinium trichloroacetate (GTCA) crystal was synthesised and grown by using slow evaporation solution growth technique from mixed solvent. The grown crystal was characterized by single crystal X-ray diffraction (SXRD) and powder X-ray diffraction (PXRD) analysis. Fourier transform infrared (FTIR) spectrum of GTCA was recorded and the frequency assignments of various functional groups were compared with theoretical values. Mechanical strength of the grown crystal was studied using Vickers micro hardness tester. Thermal stability was studied using TG/DTA analyser. UV-Vis-NIR spectrum was recorded and the band gap energy was calculated. Geometry optimizations, first order hyperpolarizability, HOMO-LUMO energy gap, global reactive constants, thermodynamic properties, molecular electrostatic potential (MESP) and charge population were computed using B3LYP/6-31 G(d,p) basis set and DFT method and analysed.
 
 KEY WORDS: PXRD, FTIR, TG-DTA, DFT, NBO, Charge population
 
 Bull. Chem. Soc. Ethiop. 2023, 37(4), 1033-1045. 
 DOI: https://dx.doi.org/10.4314/bcse.v37i4.18

Design, synthesis and characterization of a novel oxygen-containing heterocycle crystal with NLO properties

A new NLO chalcone crystal 1-(2-furyl)-3-(4-methylthio phenyl)-2-propen-1-one (FTMS) was successfully designed and the crystal was grown by slow evaporation solution growth technique. The cell data and structure refinement were determined from the single crystal X-ray diffraction. It was found that the SHG efficiency intensity of FTMS was 18 times that of KDP. The thermal decomposition temperature of FTMS was observed at 235 ℃. The crystal has a high transmittance (95%) in 500–2000 nm with a cutoff wavelength of 405 nm.

Growth and Investigation Studies of Pure and Glycine Doped Zinc Tris-thiourea Sulphate (ZTS) Single Crystals

Abstract: Zinc Tris-thiourea Sulphate (ZTS) belongs to the family of semiorganics nonlinear optical materials. Good quality single crystal of pure and doped ZTS have been grown by slow evaporation solution growth technique at room temperature. The grown crystals have been subjected to FTIR and UV visible spectra studies. The Fourier Transform Infrared analysis confirms the presence of functional groups and zinc coordination in grown crystals. The UV visible spectrum revels that grown crystals were transparent in the entire visible region. These investigations indicated that impurity played an important role in the changes of the transmittance of ZTS crystals.

Crystal growth, spectroscopic, hirshfeld surface analysis, optical, and non-linear aspects of 2- methylimidazolium nitrate organic single crystal

An organic 2-Methylimidazolium nitrate (2MIN) single crystal is grown using a slow evaporation solution growth technique. Optically transparent, the colourless crystal size is 24 × 5 × 4 mm3 with well-defined morphology of the grown crystal. The Single crystal XRD and PXRD determined the lattice cell parameters of the grown crystal and identified morphology. The molecular structural form was integrated using FTIR and NMR (1H and 13C) spectroscopic analysis. Hirshfeld surface analysis was consolidated for the N–H⋯O and C–H⋯O hydrogen bonds between molecules. The grown crystal linear optical properties were confirmed with UV–Vis NIR technique. The laser utility limitation of the 2MIN crystal was expressed through laser beam irradiated LDT analysis. The thermal analysis has been used to demonstrate adequate thermal stability and melting point. The mechanical analysis quantifies the work hardening coefficient and void volume of the surface. The dielectric constant and dielectric loss were found to be intensely dependent on the temperatures and frequency of the applied electric field. Z-scan analysis was used for the calculation of the non-linear refractive index (n2), non-linear absorption (β), and third-order non-linear susceptibility (χ3).

Synthesis, crystal growth, structural and physicochemical properties of N-methylurea benzoic acid single crystal for non-linear optical applications

The organic single crystal of N-methylurea benzoic acid (NMUB) was synthesized and successfully grown from a slow evaporation solution growth technique for the first time in literature. The structure of the NMUB single crystal was analyzed by Single crystal X-ray diffraction (SCXRD); the crystallization of the NMUB crystal was a monoclinic crystal system with the space group P21/c. The crystal structure was combined by the carboxylic groups of H- atoms in benzoic acid with protonated N-methylurea anions. The FTIR and 1H, 13C NMR chemical shifts were analyzed by distinct vibrational groups and molecular structures. The PXRD ascertains the grown crystal crystallographic planes and crystalline nature. The Hirshfeld surfaces analysis determines the theoretical inter and intra-molecular interaction with the aid of color coding. The UV-Vis NIR spectra revealed the low absorption edge, and the optical band gap was anticipated. The crystal thermal and mechanical stability was analyzed by TG/DTA, Vickers microhardness, and void volume. The laser utility limitation for the crystal was determined through laser beam irradiated LDT analysis. The third-order optical non-linear parameters were determined from the z-scan technique.

Hydrogen-bonded structure and optical nonlinearities in the proton-transfer complex of 8-hydroxy-5-nitroquinoline with ρ-toluenesulfonic acid

Single crystals of 8-hydroxy-5-nitroquinolinium p-toluene sulfonate (HNT) were grown by the slow evaporation solution growth technique. The structure was elucidated by single-crystal X-ray diffraction analysis, and the crystal belongs to the monoclinic system with the space group C2/c. The crystallinity of HNT was studied by powder X-ray diffraction analysis. The presence of functional groups was determined by FT-IR spectral analysis. The band gap energy is estimated by the application of the Kubelka–Munk algorithm. The charge transfer characteristic of the compound was studied by frontier molecular orbital (FMO) analysis. The first-order hyperpolarizability of the HNT molecule was found to be 285.45 × 10−30 esu, which is ~ 750 times higher compared to the reference urea molecule. Investigation of the intermolecular interactions and crystal studies packing via Hirshfeld surface analysis, based on single-crystal XRD, reveals that the close contacts are associated with molecular interactions. Fingerprint plots of the Hirshfeld surfaces were used to locate and analyze the percentage of hydrogen-bonding interactions. The Mulliken charge of the present molecule was theoretically analyzed. The Kurtz-Perry powder technique has been used to estimate the second harmonic generation. Observed small SHG and large hyperpolarizability are rationalized.

Lead-free double perovskite Cs2MBiCl6 (M = Ag, Cu): insights into the optical, dielectric, and charge transfer properties.

Recently, double perovskites have shown excellent potential considering the instability and toxicity problems of lead halide perovskites in optoelectronic devices. Here, the double perovskites Cs2MBiCl6 (M = Ag, Cu) were successfully synthesized via the slow evaporation solution growth technique. The cubic phase of these double perovskite materials was verified through the X-ray diffraction pattern. The investigation of Cs2CuBiCl6 and Cs2AgBiCl6 utilizing optical analysis showed that their respective indirect band-gap values were 1.31 and 2.92 eV, respectively. These materials, which are double perovskites, were examined using the impedance spectroscopy technique within the 10-1 to 106 Hz frequency and 300-400 K temperature ranges. Jonncher's power law was utilized to describe AC conductivity. The outcomes of the study on charge transportation in Cs2MBiCl6 (where M = Ag, Cu) suggest that the non-overlapping small polaron tunneling mechanism was present in Cs2CuBiCl6, whereas the overlapping large polaron tunneling mechanism was present in Cs2AgBiCl6.

Growth, optical, dielectric and mechanical studies in ferroelectric bis(methyl ammonium) tetrachlorocadmate single crystal

The bis(methylammonium) tetrachlorocadmate (MAC-Cd) single crystal was synthesized using the slow evaporation solution growth technique at ambient temperature. The grown crystal is subjected to single-crystal X-ray diffraction, Fourier transform infrared spectroscopy (FTIR), UV–vis analysis, dielectric, and mechanical study. The presence of various functional groups was confirmed by FTIR spectrum. UV–Vis spectrum analysis was used to investigate the transparency of the crystal, and the cut-off wavelength was determined to be 235 nm. Detailed dielectric study was carried out to investigate the dielectric behaviour of the title crystal. The empirical formula was utilized to theoretically assess solid-state characteristics such as valence electron, plasma energy, Penn gap, and Fermi energy for MAC-Cd and estimated values were used to compute electronic polarizability. Vickers microhardness test was performed to measure mechanical stability and the effect of indentation size was investigated using various models.

Crystal structure, vibration spectra, antibacterial and non-linear optical properties of a picrate based on triphenylphosphinium dication

An organic crystal, 1,4-phenylenebis(methylene)-bis(triphenylphosphinium) picrate (abbreviated as [TPPBzTPP][PIC]2) was grown by a slow evaporation solution growth technique and characterized by elemental analysis, spectroscopy, thermal analysis, powder and single crystal XRD. The new picrate crystallize in triclinic space group P−1 and consists of [TPPBzTPP]2+ cation and two picrate anions. Experimental vibrational bands (IR and Raman) have been discussed and assigned. The HOMO-LUMO energy gap explains the charge transfer interaction in the molecule. TG-TDA technique reveals that the material was stable up to 280.7 °C. In addition, [TPPBzTPP][PIC]2 showed good antibacterial activities against Escherichia coli and Staphylococcus aureus. The results of DFT calculation indicated that the first hyperpolarizability value (βtot) of the crystal is 20.85 times that of KDP, which exhibited good nonlinear optical properties.

Synthesis, structure, Hirshfeld surface analysis, and computational studies of 2-amino-5-nitropyridine-2,4-dinitrophenol cocrystal

A supramolecular cocrystal of 2-ammino-5-nitropyridine (ANP) with 2,4-dinitrophenol (DNP) has been successfully grown by the slow evaporation solution growth technique. The crystal structure of 2-amino-5-nitropyridine-2,4-dinitrophenol (ANDP) was elucidated by the single-crystal X-ray diffraction analysis, and it belongs to a monoclinic system with centrosymmetric space group P21/n. The bulk phase purity and homogeneity of the material were confirmed by powder X-ray diffraction analysis. The functional groups present in the molecule are identified by FT-IR analysis, and the band gap energy was estimated using diffuse reflectance data by the application of the Kubelka–Munk algorithm. The thermal stability of the compound was investigated by carrying out TG–DTA analysis. Theoretical calculations were performed using the density functional theory method to derive the dipole moment and hyperpolarizability. The high value of first-order molecular hyperpolarizability (β) suggests that it is a potential microlevel NLO candidate.

Synthesis, growth and characterization of magnesium chloride doped L-alanine cadmium chloride single crystal: For nonlinear optical application

The aim of this research was to synthesize and characterize pure and magnesium chloride (MgCl2) doped L–alanine cadmium chloride (LACC) single crystals. Pure and MgCl2 doped LACC single crystals were synthesized by solution method with slow evaporation solution growth technique at room temperature. The single crystal X-ray diffraction studies of pure, 1 and 2 mol% MgCl2 doped LACC single crystals revealed monoclinic crystal structure with C2 space group. The optical properties of pure and MgCl2 doped LACC single crystals investigated by UV–VIS/NIR spectrometer confirmed that the crystals were transparent in the wavelength range of 230-1100 nm. The optical band gap energy of pure and doped LACC single crystals were found to have the same value of 5.4 eV. The energy-dispersive X-ray analysis indicated the incorporation of magnesium and chlorine atoms in LACC single crystal. The second harmonic generation efficiency of 1 and 2 mol% MgCl2 doped LACC crystals were analyzed by Kurtz-Perry powder technique and found to be 1.75 and 2 times greater than that of the standard potassium dihydrogen phosphate crystal, respectively.

Analysis of various properties of l-alaninium p-toluenesulfonate single crystal for nonlinear optical applications

L-alaninium p-toluenesulfonate single crystal is a promising organic nonlinear optical material for second harmonic generation (SHG) and optical limiting applications. In this work, the slow evaporation solution growth technique was employed to grow a good quality single crystal at ambient conditions. The obtained crystal’s structure, unit cell dimensions and phase identification were done by Powder X-ray diffraction (PXRD) and found that it crystallizes in orthorhombic structure with space group P212121 and exhibits non-centrosymmetric nature. Its crystalline purity was characterized by High-Resolution X-ray diffraction (HRXRD) and found highly crystalline with minor grain boundaries. The Hirschfield surface analysis was carried out to identify major interactions. The photopyroelectric (PPE) technique was employed to determine the specific heat capacity (Cp) and thermal conductivity (k) of the grown sample. A low value of inhomogeneity in the birefringence of the titled crystal suggests its better optical quality. Photo-conductivity studies inferred that the titled compound features negative photoconductivity and the currents produced were in nanoscale. Further, the Piezoelectric coefficient (d33) was also measured. The mechanical strength was studied by giving shock waves to the crystals in terms of shock damage threshold (SDT) and by giving static indentations to the crystals in Vickers’s microhardness test. The third-order nonlinear optical properties were studied by Z-scan analysis.

Growth and characterization of nitrophenol complexes with piperazine and pyridine derivatives

1-amino-4-methyl piperazine bis (4-nitrophenol) (1A4MP4N) and 2-amino-5-methyl pyridinium 4-nitrophenolate 4-nitrophenol (2A5MP4N) have been grown as single crystals using slow evaporation solution growth technique at room temperature. The grown crystals were characterized by single crystal X-ray diffraction and its lattice parameters were determined. 1A4MP4N and 2A5MP4N were crystallized in monoclinic crystal system with P21/n and Cc space group respectively. In 1A4MP4N, piperazine ring possesses inversion symmetry and has a chair conformation. Piperazine ring linked to 4-nitrophenol molecule through O3-H3D···N2 hydrogen bond forms C(5) chain motif. In 2A5MP4N, N1 atom in 2-amino-5-methyl pyridinium cation is connected with 4-Nitrophenolate anion through N1-H1···O11 hydrogen bond thus forms C(12) chain motif. Hirshfeld surface mapping analysis is carried out for both crystal structures. The fingerprint plot for H···H intermolecular contacts cover a major portion (41 %) of the Hirshfeld area of 1A4MP4N and O···H (35.7%) intermolecular contacts play a major role in 2A5MP4N. The Taucs plot reveals that band gaps of 1A4MP4N and 2A5MP4N are 2.66 eV and 5.18 eV respectively. From Z-scan technique the third order nonlinear optical susceptibility is found to be χ3 = 1.21322 × 10−9 esu and 1.75752 × 10−9 for both crystals.

Synthesis, structural characterization, and Hirshfeld surface analysis of novel NLO active 1-methyl-1,3,5,7-tetraazaadamantan-1-ium 3-carboxy-5-nitrobenzoate hydrate

Single crystals of 1-methyl-1,3,5,7-tetraazaadamantan-1-ium 3-carboxy-5-nitrobenzoate hydrate (I) were grown from an aqueous solution containing hexamethylenetetramine (HMT) and 5-nitroisophthalic acid (5NIPA) by slow evaporation solution growth technique after the mild hydrothermal process. The crystal structure is elucidated by single-crystal X-ray diffraction analysis. It crystallizes in the monoclinic system with acentric space group Cc. The cation and anion present in the adduct are bridged by a water molecule, which is interconnected with CH···O and OH···O hydrogen bonds. The relative second harmonic generation (SHG) efficiency measurements characterized by the Kurtz powder technique reveal that (I) is an active SHG material. The grown crystals were further characterized by FT-IR, UV-DRS, and photoluminescence spectral analysis. Theoretical calculations were performed using density functional theory to derive the dipole moment, polarizability, and first-order molecular hyperpolarizability (β). The intermolecular hydrogen bonding interactions are analysed by Hirshfeld surface analysis and fingerprint plots. Theoretically estimated high β rationalized by the experiment. The molecular electrostatic potential (MEP) maps and Mulliken atomic charge were calculated using density functional theory (DFT) calculations.

Synthesis and characterization of nonlinear optical metal organic frame work – Cadmium di glycinate monohydrate

The new non-linear optical single crystal of Cadmium di glycinate monohydrate have been synthesized by the slow evaporation solution growth technique and it was characterized by SXRD,powderXRD,SEM, FTIR, UV-Vis-NIR, TG/DTA and SHG measurements. In the polymeric structure the metal ion Cd (II) has coordinated with carboxylate oxygen atom and glycine ligand nitrogen atom. The crystalline nature of the material was proved by PXRD pattern. The lattice strain produced by the bimetallic cadmium is found to be 0.0042. The functional groups are confirmed by FTIR analysis, again the force constant of C-C bond was enhanced to 316 Nm−1. The UV-Visible spectrum reveals the optical qualities such as band gap, transmittance and refractive index of the grown crystal. The lower cut off wavelength was found to be 213 nm. The TG-DTA analyses were carried out to determine the thermal stability as well as the decomposition temperature. The Cadmium-Glycine frame work shows void morphology. The title compound shows superior SHG efficiency compared to standard KDP.

Effect of shock wave on optical properties of Propyl p-hydroxybenzoate single crystal: A self-defocusing third order nonlinear optical material

This work focuses on the effect of shock wave on optical properties of propyl p-hydroxybenzoate single crystal. An optically transparent single crystal was grown by adopting slow evaporation solution growth technique (SEST). Its structure was confirmed by powder X-ray diffraction using Reitveld refinement. The Hirshfeld surface morphology and the intermolecular interaction of titled compound was scrutinized using crystal explorer. Three shock waves generated at constant air compressor pressure of 0.78 Mpa with calculated Mach number 1.7 were allowed to interact with the grown crystal. The UV–vis spectroscopy analysis on shock wave treated sample shows an increase in transmittance for 1st and 2nd shock and a reduction of transmittance for the 3rd shock wave. The defects induced after each shockwave – sample interaction was investigated by photoluminescence spectroscopy and surface morphology studies in detail. The third order nonlinear properties like self – defocusing and reverse saturation absorption of grown crystal were studied using a femto-second Ti-sapphire laser source. The nonlinear absorption coefficient, refractive index were calculated to be 4.04 ˟ 10−10 cm/W and −8.47 ˟ 10−15 cm2/W using open and closed aperture Z-scan measurement respectively.

Syntheses, crystal structures, optical properties, antibacterial activity and DFT calculations of two substituted benzyl triphenylphosphinium picrates

Two new organic hybrid materials, namely, 4-chlorobenzyl triphenylphosphinium picrate and 4-iodobenzyl triphenylphosphinium picrate [4ClBzTPP][PIC](1) and [4IBzTPP][PIC](2), have been grown by slow evaporation solution growth technique and characterized by elemental analysis, spectroscopy, thermal analysis, powder and single crystal XRD. Two new picrates crystallize in triclinic space group P−1 and consist of a pair of [4ClBzTPP]+/[4IBzTPP]+ cations and picrate anions. The one-dimensional anionic chain are constructed by the non-bonded O···O and N···O interactions. Experimental vibrational bands (IR and Raman) have been discussed and assigned. The HOMO-LUMO energy gap explains the charge transfer interactions in the molecules. TG-TDA technique reveals that two materials were stable up to 215 °C and 253 °C, respectively. Excited by 250 nm ultraviolet light, two materials emit main luminescent emissions bands at about 374 nm and 524 nm in solid state at room temperature. In addition, two picrates show good antibacterial activities against Escherichia coli and Staphylococcus aureus. The results of DFT calculations based on the structures of 1 and 2 indicate that the first hyperpolarizability value (βtot) of two crystals are 5.8 and 32.3 times that of KDP, respectively, which show good nonlinear optical properties.

Growth and characterization of DL-Norleucine maleate crystals

To obtain the single crystals of DL-Norleucine Maleate (DLNM), slow evaporation solution growth technique was used. The good crystalline quality of the crystal was validated by the diffraction peaks of the Powder X-Ray diffraction techniques. The functional groups which are present in the crystal were validated by FTIR and FT Raman method. Density functional theory (DFT) computation gives optimized structure parameters of DLNM molecule. The compound is changeless thermally up to 160°C and it is illustrated by TG-DTA thermal studies. The composition of the DLNM crystal was studied by EDAX spectroscopy. NMR spectral and chemical shifts of the grown crystal of DLNM were analyzed. The study of Vickers micro hardness study leads to the hardness number (HV) evaluation and work hardening coefficient. Various dielectric parameters like AC conductivity, dielectric constant and loss energy of the sample were determined from the dielectric studies.

Enhanced antimicrobial activity and physicochemical properties of an organic nonlinear optical crystal: L-tryptophan l-tryptophanium bromide (LTTB) for biomedical applications

A good quality biologically active single crystal of l -tryptophan l -tryptophanium bromide (LTTB) with molecular formula C 22 H 27 BrN 4 O 5 was successfully synthesized and grown from aqueous solution using slow evaporation solution growth technique. The synthesized crystal was subjected to various characterization techniques. Single crystal XRD study revealed that the grown crystal corresponds to monoclinic system of space group P2 1 and its crystallinity was tested by powder XRD analysis. The elemental composition of LTTB was confirmed by EDS analysis. The optical characteristics of the synthesized crystal were assessed by UV–Vis-NIR and Photoluminescence analyses. Moreover, the frequency dependent optical constants were computed and discussed in detail. The mechanical strength and the mechanical factors of the synthesized crystal were calculated based on Vickers microhardness test. The thermal stability and its characteristics were computed by TG-DTA-DSC analysis. Dielectric studies of LTTB were observed at various frequencies and temperature. The nonlinear optical performance of the synthesized crystal was examined by Kurtz-Perry technique. The antimicrobial capacity of the synthesized crystal was tested in-vitro against various bacterial and fungal species by Kirby-Bauer agar disk diffusion technique. The susceptibility test showed that the compound has the greatest activity against Aspergillus Niger and Staphylococcus aureus. Finally, all of these studies suggested that LTTB might be useful in biomedical and nonlinear optics applications.

Impedance spectroscopic study of charge transport and relaxation mechanism in the lead-free hybrid perovskite CH3NH3CuCl3

In the field of commercialization, organic–inorganic hybrid perovskite materials are becoming more popular these days in view of their prospective use in solar cells and also in other optoelectronic applications. In this paper, a non-toxic CH3NH3CuCl3 (MACuCl3) hybrid perovskite is successfully synthesized via the slow evaporation solution growth technique. The monoclinic phase of the material is checked using the X-ray diffraction measurement. The chemical composition of the prepared compound is discussed by a scanning transmission electron microscope coupled with the energy dispersive X-ray spectroscopy (STEM-EDS). Such systematic characterizations as differential scanning calorimetry (DSC) measurements and dielectric measurements indicate that MACuCl3 goes through a reversible phase transition at T1 ≈ 350/352 K MACuCl3 demonstrates a semiconducting property with a direct band gap value of approximately 2.54 eV. Over the 10−1-106 Hz frequency range, the dielectric constant, the loss factor, the electric modulus and also the electrical conductivity of MACuCl3 show strong temperature dependence. The Nyquist plot confirms the various contributions of grains and grain boundaries to the total impedance. In the high-frequency region, the dielectric constant tends to increase with temperature. The modified Cole–Cole plot asserts that while the relaxation time decreases with the rise in temperature, the space charge and free charge conductivity increase the moment the temperature climbs. In accordance with the modified Kohlrausch-Williams-Watts (KWW) equation, an asymmetrical nature corresponding to the non-Debye type of the perovskite is noticed in the electric modulus spectra at different temperatures. Moreover, the imaginary part of the electric modulus spectra is found to shift from the non-Debye toward the Debye type with the increase in temperature despite not getting the exact Debye response and emerging as a semi-conductor material. The study of the charge transfer mechanism of MACuCl3 is carried out based on Elliott's theory. The conduction mechanism in MACuCl3 is interpreted through the following two approaches: the overlapping large polaron tunneling (OLPT) model (phase 1) and the non-overlapping small polaron tunneling (NSPT) model (phase 2). Moreover, the high dielectric constant of MACuCl3 which is associated with a low dielectric loss makes it a possible candidate for energy harvesting devices.