Search

A quinoline derivative, 4‐(quinolin‐2‐ylmethylene)aminophenol was synthesized and structurally characterized by single crystal X‐ray diffraction. The crystal packing behavior and intermolecular interactions were examined by Hirshfeld surface analyses, 2D fingerprint plots and QTAIM analysis. The second order nonlinear response of 4‐(quinolin‐2‐ylmethylene)aminophenol molecule immersed in DMSO was investigated at PCM/DFT/CAM‐B3LYP/6–311++G(d,p) level. Theoretical calculations of the Hyper‐Rayleigh scattering (HRS) first hyperpolarizability were performed using two different procedures, the Sum‐over‐states scheme and the energy derivative method from Gaussian16. The HRS first hyperpolarizability results were compared with obtained for other organic compounds and shown that the 4‐(quinolin‐2‐ylmethylene)aminophenol presents a good nonlinear optical response. [ABSTRACT FROM AUTHOR]

Two new isostructural halogenated dihydroquinolinones were synthesized and characterized by single crystal X-ray diffraction. A detailed isostructural analysis of the electronic and optical properties is presented using density functional theory models with emphasis on the structure–property relationship in the solid phase. The physicochemical properties such as molecular electrostatic potential, frontier molecular orbitals as well as the nature of intermolecular interactions and the interaction energy of dimeric structures are almost unaffected by the replacement of the bromine atom by the chlorine atom. Starting from the embedded unit cells, the third-order nonlinear susceptibility (χ(3)) of the newly synthesized crystals has been estimated using an iterative electrostatic scheme, in which the surrounding molecules are represented by point charges. Theoretical results illustrate the role played by the environment polarization effect and halogenated substituents on χ(3) which has the same order of magnitude as those observed in other organic crystals. Our findings suggest that the dihydroquinolinone derivative crystals are very promising NLO materials. [ABSTRACT FROM AUTHOR]

A novel 4(1H) quinolinone derivative (QBCP) was synthesized and characterized with single crystal X-ray diffraction. Hirshfeld surfaces (HS) analyses were employed as a complementary tool to evaluate the crystal intermolecular interactions. The molecular global reactivity parameters of QBCP were studied using HOMO and LUMO energies. In addition, the molecular electrostatic potential (MEP) and the UV-Vis absorption and emission spectra were obtained and analyzed. The supermolecule (SM) approach was employed to build a bulk with 474,552 atoms to simulate the crystalline environment polarization effect on the asymmetric unit of the compound. The nonlinear optical properties were investigated using the density functional method (DFT/CAM-B3LYP) with the Pople's 6-311++G(d,p) basis set. The quantum DFT results of the linear polarizability, the average second-order hyperpolarizability and the third-order nonlinear susceptibility values were computed and analyzed. The results showed that the organic compound (QBCP) has great potential for application as a third-order nonlinear optical material. [ABSTRACT FROM AUTHOR]

The present work reports an analysis of the structure, spectroscopic signatures, nonlinear optical properties and docking studies of synthesized 3-(2-amino-2-oxoethyl)-5-methylhexanoic acid (abbreviated as AOEMHA) with the empirical formula C19H17NO3. The structure in the solid state determined by the single crystal X-ray diffraction technique revealed that AOEMHA is Y-shaped with the methine carbon atom acting as a junction point. The dihedral angles between the three segments forming the Y-shaped structure are 77.7(3)°, 86.2(9)° and 19.9(2)°. In the crystal structure, the O–H⋯O and N–H⋯O hydrogen bonded chains result in an infinite two-dimensional architecture parallel to the ac-plane. Intermolecular interactions were further visualized and topologically analyzed (using the quantum theory of atoms in molecules) with the support of the Crystal Explorer and Multiwfn program. The reactivity parameters (the frontier molecular orbital, molecular electrostatic surface potential, atomic charges and Fukui function) and topological studies (localized orbital locator and electron localization function) were also estimated for the investigated compound. For hydrogen and all the other single acyclic bonds, bond dissociation energy calculations have been performed to assess the possible degradation properties by the autoxidation mechanism. The linear refractive index and the third-order nonlinear susceptibility (χ(3)) are calculated as a function of the electric field frequency by using the supermolecule approach (SM) at the DFT/CAM-B3LYP/aug-cc-pVTZ level for analyzing the nonlinear optical properties in a simulated crystalline environment. The χ(3) value for the AOEMHA crystal at ω = 0.086 a.u. is significant when compared to experimental results from other organic crystals which demonstrate the opportunities for the AOEMHA crystal as a nonlinear optical (NLO) material. Molecular docking studies were performed with AKR1C3 inhibitors for the AOEMHA compound. [ABSTRACT FROM AUTHOR]

Copyright of Revista Colombiana de Química is the property of Universidad Nacional de Colombia and its content may not be copied or emailed to multiple sites or posted to a listserv without the copyright holder's express written permission. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.)

In this work, the density functional theory (DFT) calculation combined with a polarizable continuum model (PCM) was used to study the solvent media effects on the electrical and geometrical behaviors of the Schiff-base derivative, (E)-4-[({4-[(pyridin-2-ilmetilideno)amino]phenyl}amino)-metil]fenol (EPAF). The linear and nonlinear optics parameters, as the dipole moment, linear polarizability, and first and second hyperpolarizabilities, were calculated at DFT/B3LYP/6-311+G(d) level, for the EPAF molecule in several solvent media. The dynamic behavior of the Hyper-Rayleigh Scattering (HRS) first hyperpolarizability was studied as function of the electric field frequency. The results presented for HRS first hyperpolarizability suggest that the studied crystal has good nonlinear optical properties. In addition, the gap energy was calculated from the HOMO-LUMO energies difference in several solvent media. The EPAF crystal intermolecular interactions were studied by the Hirshfeld surface analysis. The third-order electric susceptibility χ(3) of the crystal EPAF was also calculated, indicating the EPAF crystal as a promising candidate for NLO applications in photonic and optoelectronic devices. [ABSTRACT FROM AUTHOR]

In this article, we study the electric properties of two coumarin derivatives whose difference stems from the change of substituents at 3-position of the pendant benzene ring (C18H15NO3) and (C18H15NO4). We use the supermolecule approach to deal with the molecules under the effect of the crystalline environment to calculate dipole moment, linear polarizability, and second-order hyperpolarizability, for the isolated and embedded molecules, including the static and dynamic cases and the presence of solvents. The (hyper) polarizabilities were derived from an iterative process and an ab initio computational procedure. In addition, we also calculated the HOMO-LUMO energies; at this point, the objective is to verify the effect of the exchange of substituents on the Band-Gap energy, an important parameter related to the excitation properties of coumarin compounds. [ABSTRACT FROM AUTHOR]

We investigate the short-range correlation effects of plasmon-phonon collective excitations in a quantum well wire by using the self-consistent field approximation theory proposed by Singwi, Tosi, Land and Sjolander [Phys. Rev. 176, 589 (1968)]. In our calculation model, we consider a three-subband model with only one populated, for a rectangular cross-section quantum well wire with infinite height for the potential barrier. We have verified that by decreasing the wire width (and/or decreasing the electronic density), the local field correction effects are increased. We compare the present results with those obtained within the Random Phase Approximation throughout the paper and found that the differences between the two calculation methods are more significant for the intrasubband plasmon. [ABSTRACT FROM AUTHOR]

We report a study of the structural and electrical properties of a carboxylic acid derivative (CAD) with structural formula C5H8O2 ((E)-pent-2-enoic acid). Using the Møller-Plesset Perturbation Theory (MP2) and the Density Functional Theory (DFT/CAM-B3LYP) with the 6-311++G(d,p) basis set the dipole moment, the linear polarizability and the first and second hyperpolarizabilities are calculated in presence of static and dynamic electric field. Through the supermolecule approach the crystalline phase of the carboxylic acid derivative is simulated and the environment polarization effects on the electrical parameters are studied. Static and dynamic estimation of the linear refractive index and the third-order nonlinear susceptibility of the crystal are obtained and compared with available experimental results. The characteristic vibrational modes and functional groups present in CAD were analyzed by Fourier Transform Infrared Spectrum (FT- IR) in the region of 400-4000 cm-1. Through the Hirshfeld surface analysis the molecular structure and the vibrational modes properties of the CAD crystal are explored. The effects of solvent medium on the molecular properties are taken into account through the Polarizable Continuum Model (PCM). Also, the frontiers molecular orbitals, the band gap energy, and the global chemical reactivity descriptors are discussed. All the properties studied suggest that the present material may be considered for nonlinear optical material. [ABSTRACT FROM AUTHOR]

Recently a noncentrosymmetric single crystal of a dibenzoate derivative, namely, dimethyl-4,4'-(methylenebis(azanediyl))dibenzoate, with second harmonic generation activities at 405 nm and ultrafast self-healing activity was reported by Mondal et al. in Nature Communications in 2023. Here, the linear and nonlinear optical properties of this notable molecular crystal were simulated using 1,611,464 atoms in the Supermolecule approach at the DFT/CAM-B3LYP/aug-cc-pVTZ level. Our results for the second order nonlinear optical properties of dimethyl-4,4'-(methylenebis(azanediyl))dibenzoate show that the second harmonic generation is more significant at 532 nm. In addition, the density functional theory calculations of the electro-optical parameters for the crystals in the pristine state and after the fracture mechanical self-healing process show small differences, confirming the efficiency of the self-healing process. Additionally, the crystal displays significant third-order nonlinear optical properties, particularly pronounced at a shorter wavelength of 330 nm. Thus, the self-healing dimethyl-4,4'-(methylenebis(azanediyl))dibenzoate crystal shows relevant second and third order nonlinear optical properties which make it a very interesting material for optical applications., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

In recent years, scientists have been very interested in single crystals of monoaromatic compounds with mechanical softness, but they are hard to find. The present work reports a comparative study of structural, spectroscopic, and quantum chemical investigations of three structurally similar mechanically bending monoaromatic compounds, namely, 2-amino-3-nitro-5-chloro pyridine (I), 2-amino-3-nitro-5-bromo pyridine (II), and 2-amino-3-nitro-5-iodo pyridine (III). The mechanical responses of the three organic crystals studied here are very intriguing due to the similarity of their chemical structures, which only differ in the presence of halogen atoms (Cl, Br, and I) at the fifth position of the pyridine ring and are explained through examining intermolecular interaction energies from energy frameworks analysis, slip layer topology, and Hirshfeld surface analysis. The crystals of all the three feature one dimensional ribbons comprising alternating N amino H⋯O nitro and N amino H⋯N pyridine hydrogen bonds that form R 2 2 (8) dimeric rings, respectively. In (III), weak I⋯I interactions link the adjacent ribbons forming a two dimensional sheet. Layer-like structures are observed in all three crystals, with no significant interactions between the adjacent architectures (ribbons or sheets). Energy framework calculations are used for estimating the bending ability of the three compounds, with the three following the order Cl ≪ Br < I. The iterative electrostatic scheme coupled with the supermolecule approach (SM) at the DFT/CAM-B3LYP/aug-cc-pVTZ level is used to calculate the third-order nonlinear susceptibility (χ 2 ) values in a simulated crystalline environment for the static case as well as two typical electric field frequency values, (λ = 1064 nm) and (λ = 532 nm). In addition, estimates of the topological studies (localized orbital locator and electron localization function) and reactivity characteristics (global reactivity parameters, molecular electrostatic potential, and Fukui function) are made for the compounds under investigation. Docking studies done using AutoDock software with a protein target (PDB ID: 6CM4) revealed that three compounds could be used to treat Alzheimer's disease.2 (8) dimeric rings, respectively. In (III), weak I⋯I interactions link the adjacent ribbons forming a two dimensional sheet. Layer-like structures are observed in all three crystals, with no significant interactions between the adjacent architectures (ribbons or sheets). Energy framework calculations are used for estimating the bending ability of the three compounds, with the three following the order Cl ≪ Br < I. The iterative electrostatic scheme coupled with the supermolecule approach (SM) at the DFT/CAM-B3LYP/aug-cc-pVTZ level is used to calculate the third-order nonlinear susceptibility (χ 3 ) values in a simulated crystalline environment for the static case as well as two typical electric field frequency values, (λ = 1064 nm) and (λ = 532 nm). In addition, estimates of the topological studies (localized orbital locator and electron localization function) and reactivity characteristics (global reactivity parameters, molecular electrostatic potential, and Fukui function) are made for the compounds under investigation. Docking studies done using AutoDock software with a protein target (PDB ID: 6CM4) revealed that three compounds could be used to treat Alzheimer's disease., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier B.V. All rights reserved.)