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A new organic nonlinear optical (NLO) material 2-(6-chloropyridin-3-yl)-N'-(2,3-dihydro-1,4-benzodioxin-6-ylmethylidene)acetohydrazide (CDA) has been synthesized by reflux method. Single crystals were grown by slow evaporation technique and the crystal structure was elucidated by single crystal X-ray diffraction method. Density functional theory (D...
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Thin films of lead sulfide (PbS) are being extensively used for the fabrication of optoelectronic devices for commercial and military applications. In the present work, PbS films were fabricated onto a soda lime glass substrate by using an electron beam (e-beam) evaporation technique at a substrate temperature of 300 °C. Samples were annealed in an...
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... The -conjugation for the compounds can be Frontier molecular orbitals (FMO) provide essential information about electronic states, kinetic stability of the structure, active sites, and chemical reactivity [34], [39], [40]. The most important FMOs are at the edges of the electron's highest occupied orbitals (HOMO) and at the lowest unoccupied orbitals (LUMO) which play a significant role in chemical reactivity, optical properties, energy gap electrical characteristics, and stability of the molecule [27], [41], [42]. ...
... This feature makes these levels to be very important in the optoelectronic characteristics of the materials depending on the dynamic orbital states [40], [41], [43]. ...
... The previously determined parameters are listed in table 4. Both compounds can be considered soft materials due to the low value of , the higher value of the global hardness indicates more stability of the compound [41], thus the PCh-2 crystal is more stable than PCh-1 due to the lower bandgap of PCh-1 [47]. In soft compounds, electrons can flow easily making high ICT within a molecule which enhances the NLO characteristic [47] and give a strong indication to find a high response of NLO behavior of the studied compounds. ...
Herein, two novel pyrenyl-chalcone derivatives named PCh-1 and PCh-2 were synthesized by the Claisen-Schmidt reaction and successfully recrystallized in acetone to get single crystals. The crystals were spectroscopically characterized via SCXRD and UV-Vis absorption. Quantum computational studies including NBO, MEP, FMO, and polarity were performed using DFT at B3LYP/6-311++G (d,p). Intermolecular interactions were investigated using Hirshfield analysis while intramolecular interactions were discussed experimentally (UV-Vis absorption spectroscopy) and theoretically using TD-DFT at CAM- B3LYP/6-311++G (d,p). The presence of the intermolecular interactions of C-H…O, C-H…F, C-H…
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interactions stabilize both crystals in head-tail (PCh-1), zig-zag fashion (PCh-2), and face to face stacking. The hyper conjugative interactions extracted from NBO analysis confirmed the high stability of both crystals. The UV-Vis and FMO studies show low bandgap energy of 3.012 eV (PCh-1) and 3.047 eV (PCh-2) and opaque in the visible range revealing strong ICT. The nonlinear behavior of the compounds was investigated using the Z-scan technique via CW laser working at 637nm. An excellent NLO response in order of 10−5 esu (PCh-1) & 10−6 esu (PCh-2) and fast response in limiting optical signal at 1245.5 mW (PCh-1) & 1431.9 mW (PCh-2) are observed. The structure-property findings suggest the higher inter/intramolecular charge transfer in PCh-1 compared to PCh-2 is due to the strength of the EDG, planarity of the bone structure, and polarizability. The high NLO performance of the crystals suggests a promising application to use them as NLO material.
... Computational DFT studies for the molecules were performed using Gaussian 09 [54][55][56]. The molecule was built and visualized using Gaussview 5 program package. ...
Human epidermal growth factor receptor 2 (HER2)-positive breast cancer exhibits early relapses, poor prognoses, and high recurrence rates. Herein, a JNK-targeting compound has been developed that may be of utility in HER2-positive mammary carcinoma. The design of a pyrimidine-and coumarin-linked structure targeting JNK was explored and the lead structure PC-12 [4-(3-((2-((4-chlorobenzyl)thio) pyrimidin-4-yl)oxy)propoxy)-6-fluoro-2H-chromen-2-one (5d)] was observed to selectively inhibit the proliferation of HER2-positive BC cells. The compound PC-12 exerted DNA damage and induced apoptosis in HER-2 positive BC cells more significantly compared to HER-2 negative BC cells. PC-12 induced PARP cleavage and down-regulated the expression of IAP-1, BCL-2, SURVIVIN, and CYCLIN D1 in BC cells. In silico and theoretical calculations showed that PC-12 could interact with JNK, and in vitro studies demonstrated that it enhanced JNK phosphorylation through ROS generation. Overall, these findings will assist the discovery of new compounds targeting JNK for use in HER2-positive BC cells.
... The global hardness [η = (ELUMO − EHOMO)/2], softness (S = 1/2η), chemical potential [μ = (EHOMO + ELUMO)/2], electronegativity [χ = (I+A)/2], and electrophilic index (ψ = μ 2 /2η) were calculated by taking the energies of HOMO as ionization potential (I) and LUMO as electron affinity (A). Chemical hardness, softness, and potential were used to understand the chemical reactivity of the molecular system [50]. ...
In breast cancer (BC), STAT3 is hyperactivated. This study explored the design of imidaz-opyridine-tethered pyrazolines as a de novo drug strategy for inhibiting STAT3 phosphorylation in human BC cells. This involved the synthesis and characterization of two series of compounds namely, 1-(3-(2,6-dimethylimidazo [1,2-a]pyridin-3-yl)-5-(3-nitrophenyl)-4,5-dihydro-1H-pyrazol-1-yl)-2-(4-(substituted)piperazin-1-yl)ethanone and N-substituted-3-(2,6-dimethylimidazo[1,2-a]pyridin-3-yl)-5-(3-nitrophenyl)-4,5-dihydro-1H-pyrazoline-1-carbothioamides. Compound 3f with 2,3-dichlorophenyl substitution was recognized among the tested series as a lead structure that inhibited the viability of MCF-7 cells with an IC50 value of 9.2 μM. A dose-and time-dependent inhibition of STAT3 phosphorylation at Tyr705 and Ser727 was observed in MCF-7 and T47D cells when compound 3f was added in vitro. Calculations using density functional theory showed that the title compounds HOMOs and LUMOs are situated on imidazopyridine-pyrazoline and nitro-phenyl rings, respectively. Hence, compound 3f effectively inhibited STAT3 phosphorylation in MCF-7 and T47D cells, indicating that these structures may be an alternative synthon to target STAT3 signaling in BC.
... Therefore, the dielectric constant is maximum with higher temperatures. At higher values, the dielectric constant decreases gradually and becomes steadier due to the loss of polarization effects [64][65][66] . Furthermore, similar dielectric loss variations were observed, which could be explained by the polarization effect caused by crystal imperfections [66] . ...
The metal-organic nonlinear optical (NLO) compound Bis(4-methylbenzylammonium) tetrachloridocuprate (4MBA) was synthesized and grown by the slow evaporation method. X-ray crystal analysis revealed the crystal structure and conformation. Density functional theory (DFT) at B3PW91/LanL2DZ basis set level was applied and computed the optimized geometry, electronic structure, vibrational spectra, frontier molecular orbitals (FMO), molecular electrostatic potential (MEP), and natural bonding orbitals (NBO). UV–Vis-NIR spectroscopic measurements revealed the optical transparency range from 310 to 1100 nm and excited-state properties. The thermal behavior and stability of the compound were analyzed using TGA/DTA, and the suitability of the optical material is weighed. The dielectric parameters and AC conductivity were investigated as a function of frequency and temperature. Second-harmonic generation (SHG) efficiency was measured using the Kurtz and Perry powder approach and found 4MBA to be 0.8 times the KDP. The nonlinear refractive index (n2), nonlinear optical absorption (β) and third-order nonlinear optical susceptibility (χ⁽³⁾) measured values are 1.548 × 10⁻⁹ cm²W⁻¹, 0.0538 × 10⁻⁴ cmW⁻¹, and 6.049 × 10⁻⁸ esu respectively, and shows that the 4MBA molecule is a third-order nonlinear optical material. The optical limiting threshold value is determined as 7.632 × 10³ Wcm² for 532 nm continuous-wave laser, representing that the 4MBA is a strong candidate for the optical limiting application. The static and dynamic nonlinear optical parameters were computed with three different functions including B3PW91, M06 and PBE0 using LanL2DZ basis set. The outcomes revealed that the 4MBA molecule under study might be a promising NLO material for frequency generators and optical limiters applications.
... Nonlinear optical (NLO) crystals have grabbed the interest of scientific communities due to their promising applications, which include optical limiting, optical switching, harmonic generation, and data storage [1][2][3][4]. The tremendous applications of NLO materials have inspired scientists to design new materials with promising large molecular hyperpolarizability, γ, nonlinear absorption coefficient, β, and third order nonlinear optical susceptibility, χ (3) . ...
... The origin of nonlinearity refraction in this study is due to the thermal nature caused by the CW excitation laser source [10]. The red solid line in Fig. 10b reveals the theoretical fitting of the NLR data to extract the nonlinear refractive index, n 2 , using equation (4). The real and imaginary parts of the third-order susceptibility are computed using equations (5) and (6), respectively. ...
The presence of C-H…O and π … π stacking, which form a head to tail and face to face arrangement chain along the b-axis, was shown by single crystal analysis. The small dihedral angle between the pyrene and bromo-biphenyl rings increases the overall molecule's conjugation, and the low dihedral angles between the enone group (acceptor) and both pyrene and bromo-biphenyl moieties (donors) show the molecule's high ICT characteristic. Theoretical studies were conducted utilising density functional theory (DFT) at the B3LYP,6-311++G (d,p) basis set. ICT transfer from pyrene and bromo biphenyl moieties to carboxyl group was observed using HOMO-LUMO diagrams and Hirshfeld surfaces analysis, generating a D-π-A-π-D type push-pull system. Z-scan open and closed aperture plots were used to obtain nonlinear optical characteristics of BBPP. The self-defocusing reaction is visible in the Z-scan results, which indicate a negative nonlinear refractive index. The optical limiting behavior of the crystal is also promising. The titled crystal is a promising material for NLO devices based on the NLO characteristics of BBPP.
... From the literature survey, we noticed that there are very few reports found on optical limiting studies of organic molecules using 532 nm, 100 mW continuous-wave laser employed Z-scan technique. Recently, S. Ananda et al [59] and D. Shalini et al [60] have reported the optical limiting property of organic 2-(6-chloropyridin-3-yl)-N′-(2,3-dihydro-1,4-benzodioxin-6ylmethylidene)acetohydrazide and 4-(3-nitrophenylamino)-4-methylpentan-2-one picrate to be 2.511 × 10 3 Wcm −2 and 3.44 × 10 3 Wcm −2 , respectively. Hence, the optical limiting threshold value of the title molecule for 532 nm, 100 mW continuous-wave laser irradiation is well comparable with the literature. ...
The computation and experimental results on structural, mechanical, thermal, linear, and third order nonlinear optical properties of an organic material 4-methyl- N -((1-(4-methylbenzoyl)piperidin-4-yl)methyl)-benzamide ( 1 ) for an efficient optical limiting application with easy preparation and decent performance are presented. Its response to single-crystal X-ray diffraction allowed to investigate the molecular structure of 1 , which is optimized using computational density functional theory at the B3LYP/6-311G** level. Calculated frontier molecular orbitals and Mulliken charge are served to realize the intramolecular charge transfer in 1 and its electronegative nature responsible for optical nonlinearity. Hirshfeld analysis investigated the structural property and the magnitude of interatomic and molecular interactions to help understand structure-property relation. The FTIR and NMR spectroscopic study further confirmed the formation of 1 and the vibrational states of its functional group. The title crystal showed acceptable thermal (stable up to 130 ○ C and mechanical (stable up to 50 grams of applied load) stability, which is optimal for laser device applications. With an optical bandgap of 4.32 eV, the title material possesses much less linear optical absorption across the visible region of the electromagnetic spectrum. The nonlinear optical absorption (β), nonlinear refractive index (n 2 ) and third-order nonlinear optical susceptibility (χ ⁽³⁾ ) values are measured as (0.0139±0.001)×10 ⁻⁴ cmW ⁻¹ , (1.49±0.05)×10 ⁻¹⁰ cm ² W ⁻¹ and (4.2±0.3)×10 ⁻⁸ esu respectively shows that the title molecule is third-order nonlinear optical active. The onset optical limiting threshold value is determined as (7.092±0.01)×10 ³ Wcm ⁻² for 532 nm, continuous-wave laser irradiation indicating that the title material is a good candidate for the optical limiting application.
A new organic nonlinear optical material 7-(4-bromobenzyl)-3-(tert-butyl)-4H-[1,3,4]thiadiazolo[2,3-c][1,2,4]triazin-4-onehemihydrate (TDTZ) single crystal was grown by slow evaporation solution technique. The lattice parameters of the grown crystal were elucidated by single crystal X-ray diffraction method. The crystal structure revealed the crystallization of the compound in the monoclinic system withthe C2/c space group. UV-Vis NIR spectrum analysis deciphered TDTZ’s optical transmittance, cutoff wavelength, and bandgap. Hirshfeld surface studies were performed to understand the intermolecular interactions of the title compound. The density functional theory (DFT) using B3LYP functional with 6-311G (d,p) basis set was carried out forFrontier Molecular Orbital (FMO) analysis to estimate the transition barrier and chemical reactivity. Nonlinear optical activity wasdetermined from TDHF methods with 6-31G(d) basis sets using the GAMESS program.
Organic nonlinear optical material N'-[(E)-(5-bromofuran-2-yl)methylidene]-2-(6-chloropyridin-3-yl)acetohydrazide (BCA) was synthesized by the reflux method, and single crystals were grown by slow evaporation technique. Optical absorbance was investigated by using UV–Vis–NIR spectrophotometer and obtained the optical transmission bandwidth (200 nm to 1100 nm), lower UV cut-off wavelength (333 nm), and optical band gap (3.30 eV) parameters. The second harmonic generation (SHG) efficiency of BCA was determined using Kurtz and Perry powder technique, and it was 1.3 times greater than that of the KDP crystal. Frontier molecular orbital (FMO) analyses of BCA were performed by density functional theory (DFT) with a B3LYP/3-21G basis set. Further, the nonlinear optical static and dynamic parameters (second and third-order) were computed to demonstrate the compound's suitability for optoelectronic applications.
The quality 2-amino-5-chloropyridinium 4-aminobenzoate (2A5ClP4AB) single crystals were grown in methanol solvent by employing the solvent evaporation technique. The stoichiometry ratio of 2A5ClP4AB was confirmed by microanalysis. The melting point, decomposition, crystalline phase, purity, and specific heat capacity of 2A5ClP4AB crystal were explored by thermogravimetric-differential thermal analyses (TG–DTA), differential scanning calorimetry (DSC), and modulated scanning calorimetry (MDSC) methods. The various dielectric properties of 2A5ClP4AB single crystal concerning temperature and frequency were examined by dielectric measurements. The nonlinear optical (NLO) parameters such as dipole moment, polarizability, first-order hyperpolarizability, and second-order hyperpolarizabilities of the 2A5ClP4AB molecule were computed using density functional theory (DFT) by utilizing the Gaussian 09 program. The figured HOMO–LUMO energies of 2A5ClP4AB demonstrate the occurrence of a charge transfer mechanism, whereas the MESP map illustrates how various molecular interactions took place in it. Hirshfeld surface analyses helped to decode the nature of the interactions and packing structure of the crystals. The above studies were intended to explore the structural, thermal, electrical and NLO properties of 2A5ClP4AB and also to strengthen its effectiveness for optoelectronic and frequency conversion applications.
