NLO Activity Research Articles

Crystal Growth, Structural Elucidation, Chemical Reactivity, Topology Exploration (ELF, LOL, AIM, RDG) and NLO Activity of 4-Cumyl Phenol Crystal Using Quantum Chemical Calculation

The main objective of the study is to analyze the structural behavior and NLO activity of 4-cumyl phenol by experimental and theoretical spectroscopic techniques. Its computational result is compared with the cumene compound. The optimized structural parameters of the title compound were computationally obtained at the B3LYP/6-31G (d, p) basis set. The fundamental modes of vibration were examined by experimental FT-IR, and FT-Raman techniques. The distribution of the vibrational bands was carried out with the help of normal coordinate analysis (NCA). The resulting harmonic wavenumbers were scaled by using NCA method. Topological analysis, such as Electron localization function (ELF), natural bond orbital analysis (NBO), reduced density gradient (RDG) and atoms in molecule (AIM) analysis, molecular electrostatic potential (MEP) have been used to evaluate the intermolecular interaction, especially the hydrogen bonds. UV-visible spectrum of the compound was recorded in the region 200–900 nm and the electronic properties and HOMO-LUMO energies were calculated by time dependent density functional theory approach.

Synthesis and evaluation of the anti-TB activity of novel 7-(2-(4-substituted-phenyl)-4,5-diphenyl-1H-imidazol-1-yl)-4-methyl-2H-chromen-2-one derivatives and their DFT studies for NLO application

A series of novel 7-(2-(4-substituted-phenyl)-4,5-diphenyl-1H-imidazol-1-yl)-4-methyl-2H-chromen-2-one derivatives 5(a-g) have been synthesized and reported as anti-TB activity and non-linear optical applications. The activity results show that compounds 5b, 5c, 5d, 5f, and 5g exhibited excellent efficacy with a MIC value of 3.12 μg/mL, one-fold greater than the reference standard streptomycin (6.26 μg/mL). An in silico molecular docking study was performed against InhA protein and the results were consistent with the experimental results. Computational studies were performed using the DFT method and results reveal that the presence of greater electronegativity atoms increases the HOMO-LUMO energy gap. The NLO properties show that the presence of stronger electron-donating substituents increases the ICT, charge delocalization and β0 values. The NBO analysis shows significant interactions between LP (Lone pair), π* and σ* in compounds account for the high polarization and enhanced NLO activity.

Material synthesis, crystal structure, Hirshfeld surface and physicochemical characteristics Novel Stilbazolium crystal of 4-(2-(3-ethoxy-4-hydroxy-phenyl)-vinyl)-1-methyl pyridinium iodide (MEMPI) single crystal for NLO activity

In this study, a novel cation donor group 3-ethoxy-4-hydroxy benzaldehyde has been incorporated in the Stilbazolium cation with iodide anion to generate a new NLO activity of a single crystal of 4-(2-(3-ethoxy-4-hydroxy-phenyl)-vinyl)-1-methyl pyridinium iodide (MEMPI). The MEMPI crystal was effectively formed via the solvent evaporation technique. The structure and hydrogen bond interactions found in the molecule were determined by employing single-crystal X-ray diffraction. The compound crystallizes in the space group P21/c and monoclinic crystal pattern. The crystal structures are stabilized via intramolecular, intermolecular hydrogen bond interactions, C‒H···π, cation‒π, anion‒π, π···π stacking and lone pair-π interaction. In addition, a variety of O‒H···O, O‒H···I and C‒H···O interactions are also responsible for crystal packing. The 3D Hirshfeld surface and 2D fingerprint plots were used to examine the nature of intermolecular interaction. The 2D fingerprint maps indicate that the interactions between H···H contribute to 48.9 % of the total crystal stability. The newly synthesized material was characterized by 1H NMR and 13C NMR. In addition, the vibrational study of the synthesized molecule was performed using FTIR analysis. The grown crystal in linear optical characteristics were examined via a UV–Visible-NIR study. The photoluminescence (PL) activity of a MEMPI was studied with respect to the visible area and green colour emission was observed at 536 nm. The estimated CIE coordinates on the RGB colour gamut show the MEMPI crystal's ability to emit green light. The chemical etching approach was used to analyse the etch pit density and the growth habitat of the MEMPI crystal. The closed and open aperture Z-scan tests were carried out to determine the nature of third-order NLO susceptibility of the MEMPI crystal.

Unveiling Optical Nonlinearity: Exploring Nickel‐Curcumin Complexes through Z‐Scan and Degenerate Four Wave Mixing Techniques

AbstractTwo Curcumin (Cur) based mixed ligand complexes of Nickel have been investigated for their optical nonlinearity (NLO). Physicochemical characterization of two nickel precursors and their interaction with curcumin produced two molecules, namely Ni(C3S5)(Cur).2H2O (abbreviated as NiThCur) and NiCl(Cur)(PPh3) (abbreviated as NiTppCur). Additionally the Conceptual‐Density‐Functional‐Theory (CDFT) studies were performed. CDFT‐based optimization parameters of both molecules are theoretically interpreted. HOMO‐LUMO energy gap of NiThCur and NiTppCur were calculated 1.474 eV and 2.744 eV respectively. Both molecules demonstrated good NLO activities, studied by a Z‐scan approach and additionally with a Differential Four wave Mixing (DFWM) technique. Preliminarily investigations showed that the molecules can be potential optical limiters (OL). These studies divulge the exhibition of a 3‐photon absorption (3PA) mechanism by the synthesized molecules. NLO absorption 3PA coefficient (γ) value of 1.34×10−24 m3/W2, third‐order optical susceptibility (χ(3)) value of 1.543×10−11 esu, and the figure of merit 6.64×10−14 esu was observed for the NiThCur complex and γ=3.61×10−24 m3/W2, χ(3)=1.521×10−11 esu, and FoM=5.61×10−14 esu for NiTppCur with Z‐scan (γ and χ(3)) and DFWM methods, respectively. Normalized transmittance (NT) exhibited a decrease to 78.5 % from 100 % in NiThCur and to 69.5 % in NiTppCur. Optical limiting calculations are also presented.

Combined experimental and quantum computational studies on 5-Fluorouracil salicylic acid cocrystal: Assessment on anti-breast cancer potential through docking simulation

5-fluorouracil salicylic acid (5FUSA) cocrystal was synthesised via mechanochemical and solution evaporation technique and spectroscopic experiments and theoretical research were conducted. Methods for the experiments included XRD, FTIR, and UV spectroscopy. Following that, 5FUSA was the subject of quantum chemistry investigations employing the DFT/B3LYP/6–311++G (d, p) basis level. First, the resultant simulated XRD pattern was compared to the relevant experimental pattern. The estimated FT-IR frequencies were gathered from the same level of theory and compared to the experimental data. To learn more about the reactive properties of the 5FUSA, the molecular electrostatic potential plot was generated, and Fukui function calculations were also performed. In order to examine intramolecular interactions and verify the bioactivity of the 5FUSA molecule, the natural bond orbital study was also carried out. We examined the UV–Vis absorption wavelengths (λ) via theoretical (TD-DFT) and experimental methods. The non-linear optical properties were identified, and it was discovered that it had three times the NLO activity of urea. The inter- and intramolecular interactions of the 5FUSA were explored using the Hirshfeld surface and finger print approaches. At various temperatures thermodynamic parameters were calculated and topological analyses were conducted using the (ELF, LOL, and RDG). The anticancer activity of 5FUSA cocrystal was studied using molecular docking and the docking scores ranges between -8.1 to -9.0 Kcal/mol against breast tumor proteins.

Synthesis, Theoretical studies, and antibacterial activity of Novel Zn(II) metal complex with salicylaldehyde semicarbazone, and ortho phenylene diamine ligands.

Computational and experimental investigation of synthesized Zn(II) complex. Salicylaldehyde semicarbazone (SSC) and ortho phenylene diamine (OPDA) were the ligands for the preparation of Zn(II) metal complex. Using quantum chemistry simulations at DFT/B3LYP/LANL2DZ level of theory. FT-IR, UV, and Mass spectrometry methods were characterized the complex. The computed small gap energy demonstrated that the Zn(II) molecule had good biological activity. Measured dipole moment and first-order hyperpolarizability values were useful to investigate the complex NLO activity. Intra-molecular charge transfer, donor-acceptor transitions, and stabilization energies were determined by analyzing natural bond orbital (NBO) and Mulliken charges. Electrophilic and nucleophilic interactions were performed with the MEP map. QTAIM framework explained the nature of different intermolecular interactions within the molecule. Moreover, the ADMET studies of Zn(II) compound were also analyzed. The title molecule showed good antibacterial activity.

Growth, characterization and second harmonic generation NLO activity of semi-organic crystal: l-arginine picrate crystal doped with nickel chloride

Growth, characterization and second harmonic generation NLO activity of semi-organic crystal: l-arginine picrate crystal doped with nickel chloride

Synthesis, molecular structure, experimental and computational studies, nonlinear optical properties of amaranth dye doped L-lysine sulphate (ALLS) semiorganic crystal

A polycrystals of amaranth dye-doped L-lysine sulphate (ALLS) was synthesized and fabricated as a single crystal utilizing the solution-based growth approach and confirmed the orthorhombic structure through XRay diffraction anlaysis. The ALLS molecule was optimized in Gaussian 09 W utilizing the density functional theory (LANL2DZ/DFT) basis. Along with PED, the Fourier transform infrared (FTIR) spectroscopy helps vibrational assignments of ALLS were both theoretically and experimentally suited to one another. The FMO energies of ALLS molecules are used to derive quantum chemical parameters. To study the properties of charges existing at the molecular structure level, DOS, MESP, and MULLIKEN studies were performed. To figure out the compound's NLO activity, hyperpolarisability values are calculated. ELF, LOL, and RDG topological studies were carried out through which the localization and delocalization of electrons were found. MEP gives the relative polarity and the UV absorption gives maximum absorption at 414 nm were recorded. Additionally, ALLS's thermodynamic parameters were calculated. The NLO behaviour of the LLS complex was improved by amaranth dye, and ALLS has been suggested as a suitable compound for the fabrication of NLO devices as an outcome of both experimental and computational results.

An experimental and computational analysis on 2,6-diamine-7H-purine ligand with spectroscopic, AIM, NLO and biological activity

An experimental and computational analysis on 2,6-diamine-7H-purine ligand with spectroscopic, AIM, NLO and biological activity

Non-centro symmetric organic single crystal with NLO activity assembled by hydrogen bonding: 2-amino-6-methoxy benzothiazoleium picrate dimethyl sulphoxide solvate

Non-centro symmetric organic single crystal with NLO activity assembled by hydrogen bonding: 2-amino-6-methoxy benzothiazoleium picrate dimethyl sulphoxide solvate

In-situ Salen-type ligand formation-driven of a heterometallic Cu(II)-Hg(II) complex: Synthetic update, crystallographic features, DFT calculations, and unveil antimicrobial profiles

This article vividly describes the synthesis and structural characterization of one 6-Bromo-2-hydroxy-3-methoxybenzaldehyde ligand involving heteronuclear complex, [Cu(L)Hg(Cl)2]. X-ray single-crystal determined the complex crystal structure and characterized it by various physical methods, including elemental, FT-IR, Raman, PXRD, UV–vis, NMR, and SEM-EDX techniques. X-ray diffraction analysis reveals that the compound adopts a monoclinic space group Cc during crystallization. The crystal structure exhibits unique supramolecular interactions, like intermolecular C-H∙∙∙π H-bonding and X-bonding (X = Halogen) between Br(1) and Br(2) atoms. Hirshfeld surfaces (HS) and 2-D fingerprint plots confirm significant H…Cl (21.9 %) contacts. Further, dispersion energy dominates due to Br atoms' higher electron/electron cloud. The complex underwent DFT calculations based on the Gaussian software package at B3LYP, HF, and M062x levels, utilizing the lanl2dz, sdd, and def2tzvp basis sets. The HOMO-LUMO, ESP, Global reactivity, Interaction energy and energy frameworks, and Fukui function investigated the complex properties in a multidimensional spectrum. The complex showed promising NLO activity, which has broad technological applications. Fukui function calculation identifies regions prone to nucleophilic (Nu-) and electrophilic (E+) attacks. The complex and synthetic components were examined for antimicrobial function against Gram+ve and Gram-ve bacterial and fungal strains. Molecular docking (MD) and Protein-Ligand Interaction Profilers (PLIP) further support the antimicrobial findings.

Structural and spectroscopic investigation of 1-acetyl-2-(4-ethoxy-3-methoxyphenyl) cyclopropane and its NLO activity

To identify promising compounds and to develop a potent non-linear optical material, the molecule 1-acetyl-2-(4-ethoxy-3-methoxyphenyl) cyclopropane (AEMC) was selected. FTIR and FT-Raman spectroscopy techniques were employed to predict the functional groups and vibrational modes of AEMC. Gaussian 09 W software was utilised to analyse the parameters of the optimised title compound. Reactive sites were forecasted using MEP plots. To clarify the chemical significance of the molecule, ELF and LOL are utilised. Furthermore, the presence of interactions within the molecule is confirmed by RDG analysis. The strong and weak hydrogen bonds between the non-bonding atoms of AEMC are studied with the aid of AIM analysis. Additionally, the material's capacity to produce non-linear effects (NLO) was ascertained by examining the linear polarizability and first order hyper polarizability values.

Tricine Incorporated Potassium Metal Ion Crystal: Antibacterial and NLO Activities

Tricine Incorporated Potassium Metal Ion Crystal: Antibacterial and NLO Activities

Synthesis, solvent role (water and DMSO), antimicrobial activity, reactivity analysis, inter and intramolecular charge transfer, topology, and molecular docking studies on adenine derivative

In the current study, a molecule (E)-3-(((9H-purin-6-yl)imino)methyl)phenol (A3H) was made and its structure was characterized through the application of spectroscopic techniques. The optimization of the structure of the title chemical was performed using the B3LYP/cc-pVDZ basis set, employing the most stable conformational structure according to the DFT approach. The geometrical characteristics, vibrational wavenumbers, and electrical properties have also been investigated. The electronic characteristics of HOMO-LUMO, UV–Vis, and MEP maps were analysed, including different solvation effects. When compared to the other solvents the water has the lowest energy gap value, due to solvent interaction. The NLO activity has been investigated using the DFT/B3LYP approach, employing the cc-pVDZ basis set. In the NLO study water has the highest dipole moment, polarizability, and hyper-polarizability values. In this study, we have successfully obtained a set of lone pairs of donor–acceptor contacts and a hydrogen bond donor/acceptor surface. These findings provide a basis for explaining a charge transfer process. The utilization of molecular docking techniques has been employed to get insight into the binding interaction between the ligand and targeted proteins.

Spectroscopic, Topological and NLO Activity of N N’ Diphenyl Thiourea Acetone Monosolvate: Experimental and Theoretical Approach

The compound N,N’-Diphenylthiourea acetone monosolvate was synthesized using slow evapouration technique and characterized by FT-IR, FT-Raman, UV-visible spectra. The optimized molecular geometry (bondlength, bondangle and dihedral angle), the complete vibrational frequency were calculated by using density functional theory (DFT) B3LYP method with the help of 6-31 G(d,p) basis set. The protonated N–H…O intermolecular interaction liable for the NLO activity was deliberated using DFT method along with experimental spectroscopic techniques. The inter and intramolecular interactions accountable for the stabilization of the material was done via NBO and AIM analysis. In addition, the molecular electrostatic potential, frontier molecular orbital, global reactivity descriptors, Hirshfeld surface and 2D-fingerprint was analyzed to acquire a greater understanding of the molecular effect. UV-Vis spectrum of DPTA crystal exhibits good optical transmittance in the spectral analysis. By using spectroflurometer technique the green band region was observed in fluorescence emission spectrum. The dipole moment, polarizability, first-order hyperpolarizability (α 0), related properties (β, α 0 and Δα) and second-order hyperpolarizabilties were calculated for the identification of non-linear optical activity of the molecule. The molecular docking studies were performed to investigate the binding affinity of legend with target receptor.

Structure, chemical reactivity, NBO, MEP analysis and thermodynamic parameters of pentamethyl benzene using DFT study

This study explores the structural, molecular and electronic properties of the pentamethyl benzene (PMB) using quantum chemical calculations employing DFT/ B3LYP/6–311++G(d,p) level of theory. Structural parameters, HOMO-LUMO energies, chemical reactivity descriptors and molecular electrostatic potential (MEP) were evaluated from the optimized molecular geometry. The computed small band gap energy, correlated with the UV–visible spectrum, demonstrates that the test molecule has good biological activity. NLO activity of the molecule was also studied by evaluating dipole moment and first order hyperpolarizability values. Intra-molecular charge transfer, donor-acceptor transitions and stabilizations energies were determined from the analyses of natural bond orbital (NBO) and natural population. 1H and 13C chemical shifts were computed from the simulated NMR spectrum following GIAO approach in DMSO‑d6 solvent at the same level of DFT. Furthermore, thermodynamic parameters and rotational constants were also calculated for this molecule.

Spectroscopic characterization, DFT study, topological, molecular docking and pharmacological analysis of Iminodiacetic acid Hydrochloride

Iminodiacetic Acid Hydrochloride (IAH) optimum geometries and vibration spectra have been determined by density functional theory computations at B3LYP with 6-311++G(d, p) level basis functions. Finding the most stable structure of IAH is done through conformational analysis. In order to interpret IR and Raman spectra both quantitatively and qualitatively, vibrational spectra have been examined based on the potential energy distribution (PED) within each vibrational mode. By means of calculations both theoretical and experimental, UV–Visible and NMR spectral studies of IAH have been performed. Utilising NBO analysis, stabilisation resulting from inter- and intramolecular interaction has been studied. For predicting the reactivity and stability of the molecule, chemical reactivity descriptors are computed. Molecule size, shape, electrical potential distribution, and point of chemical reactivity will all be revealed by mapping the charge density isosurface well with electrostatic potential surface (ESP). ELF and LOL maps intended topological aspects of IAH have also been depicted. Additionally, the Natural atomic charge and the hyperconjugative interactions that cause its NLO activity have been predicted. The hyper polarizability values indicate that these compounds could be used in electro-optical applications. IAH is screened for its pharmacological activity. The binding location of the molecule to its target protein has been predicted via a molecular docking study.

DFT/TD-DFT Study of D–?–A dyes explore the NLO properties

The molecular structures and optical properties of six different N.dimethylphenylendiamino dyes were analyzed using a combination of DFT functionals (B3LYP and Cam-B3LYP/6-311+G(p,d)). The six dyes are D1-D6. The various parameters of the solvated phase, such as the polarizabilities, hyperpolarizabilities, peak absorption wavelengths, and HOMO-LUMO energy gaps, were calculated and analyzed. The results of the study are in agreement with the results of the NLO activity order thiophene linker > pyrrole bridge. Compared to the dipyrrole versions, the designed dithiophene-linker dyes exhibit longer absorption wavelengths and smaller HOMO-LUMO gaps. The predicted first hyperpolarisability of dyes D1-D3 are higher than that of D4-D5. This is mainly due to its enhanced electron-withdraw ability and the long p-conjugating action of the thiophene moiety. Highly elevated total hyperpolarisability of the designed dyes, suggests its potential application in organic NLO devices, which is expected to be useful.

Crystal growth, structural insights, spectral, Z-scan, N[sbnd]H…O hydrogen bonding interaction and non-linear optical properties of the novelly synthesized 2-aminopyridinium cyanoacetate crystal

A novel organic single crystal 2-aminopyridinium cyanoacetate (2ACY) was synthesized and analysed by using UV–Vis, FT-IR, FT-Raman and single crystal X-ray diffraction experiments. Optically transparent and defect free crystal was grown from aqueous solution by slow evaporation technique at room temperature. All theoretical computations were carried out using the density functional theory (DFT) B3LYP approach using the basis set of 6–31+G(D). The grown crystal exhibits good optical transmittance in the UV–visible spectral analysis. The thermal behaviour of the 2ACY crystal has been analysed by TG/DTA analysis. Besides, the intermolecular interactions have been inquired and revealed by NBO analysis. Intermolecular contacts and molecular surface contours were analysed by using Hirshfeld and 2D fingerprint plot analysis. Topological analysis of electron localization function (ELF), localized orbital locator (LOL) and reduced density gradient(RDG) were evaluated. Additionally molecular electrostatic potential (MEP), HOMO-LUMO and charge analysis of the title compound have been investigated. The fluorescence behaviour of 2ACY crystal has been analysed in visible region and red colour emission is evidenced at 610 nm. The outcome of SXRD, UV-visible, TG/DTA, NLO, LDT and Z-scan values were compared with earlier reported compounds and amongst which the analysed compound 2ACY show good NLO activity. The occurrence of protonated intermolecular NH…O hydrogen bonding interaction liable for the nonlinear optical activity and it was projected using theoretical along with experimental techniques.

Ionic, charge transfer interactions, reactivity of the NLO molecule morpholinium perchlorate comparison with morpholinium derivatives using DFT method

In the present study, the compound morpholinium perchlorate (MP) was explored using spectroscopic methods and quantum chemical computations. A TD-DFT method was employed to study the charge transfer ionic interaction strategy to identify the electronic transition exhibited in the UV–visible spectrum, and vibrational analysis of FT-IR and FT-Raman was also measured experimentally. Natural population analysis and molecular electrostatic potential (MEP) surface analysis of the molecule were performed to predict the molecule's reactive site. Natural bond orbital analysis (NBO) and natural charge analysis were used to study the charge transfer interaction. The nature of inter and intramolecular hydrogen bonds are analyzed by using reduced density gradient (RDG), density overlap region indicator (DORI) analysis, and Hirshfeld surface analysis. Electron localization function (ELF) and analysis provide new insight into the chemical bonding of MP. The NLO activity of the studied compound was highlighted by computing the first and second order hyperpolarizability. In the current investigation, the effects of MP and a few morpholinium derivatives were contrasted in terms of molecular geometry, vibrational assessment, HOMO-LUMO energy gap, and NLO effects. According to the results, the MP can be effectively used as an optical limiter in optoelectronics.