NLO Activity Research Articles

Antitumor and antimicrobial effect of syringic acid urea cocrystal: Structural and spectroscopic characterization, DFT calculation and biological evaluation

The syringic acid urea (SYRAUA) cocrystal was produced at room temperature using a slow evaporation approach. The SYRAUA formed as orthorhombic crystal with the Cmca space group. It was undertaken to perform structural, spectroscopic (FTIR), and optical research. For SYRAUA, the structural and different spectroscopic parameters were calculated with quantum mechanics utilizing the B3LYP/6–31++G (d, p) approach. The XRD results were related with the optimized geometrical parameters and found there is a close agreement. SYRAUA's FT-IR spectrum was analysed using the data collected in the 4000–400 cm−1 region. There is decent agreement between the calculated and recorded wavenumbers. The 200–600 nm region of the UV–Visible absorption spectrum was noted showed the presence of two absorption peaks. The NBO approach was used to analyse the charge transfer in the cocrystal, and Mulliken charge analysis was used to confirm the identity of the involved atoms. To comprehend the reactive location in SYRAUA, the molecule electrostatic potential and local reactivity descriptors were determined. The non-linear optical characteristics were determined and found that it possesses 70% NLO activity compared with urea. Hirshfeld surface and finger print analysis were used to examine the inter and intramolecular interaction of the SYRAUA. When the SYRAUA was tested for antimicrobial activity, it was discovered to have zone of clearance. Molecular docking outcomes support that SYRAUA may exhibit inhibitory activity against caspase 3,7 and 9. Amongst the three caspases the SYRAUA showed higher docking affinity to caspase 9 with the binding score of -8.4 Kcal/mol. Further the drug likeness of the SYRAUA were assessed through Lipinski's rule and the pharmacokinetic parameters and those predicted values showed good safety profile of SYRAUA cocrystal.

Substantial second‐order nonlinear optical properties of novel hexamolybdate‐julolidine hybrids: A density functional theory (DFT) study

AbstractSeries of new inorganic–organic hybrid hexamolybdate‐julolidine materials are theoretically designed and studied via density functional theory (DFT) and time‐dependent density functional theory (TD‐DFT). Their geometric and electronic structures, linear optical and second‐order nonlinear properties have also been evaluated. By the introduction of julolidine into the organoimido‐hexamolybdate, the studied systems show substantial second‐order nonlinear (NLO) responses of up to 1048 × 10−30 esu for compound 3. Upon enlarging the π‐conjugated linker, the calculated β‐responses are enhanced by a factor of 2.1. In addition, TD‐DFT calculations indicate that the strong low‐energy transition can mainly be attributed to charge transfer (CT) from julolidine‐arylimido to the hexamolybdate cluster, indicating strong communication between the POM and julolidine components, which is responsible for the linear and non‐linear optical behavior of these compounds. Ortho‐methylation to the imido‐bond has a significant effect on the stability and hence the length and linearity of the bond, although it slightly reduces the first hyperpolarizability. The whole set of results demonstrates the excellent NLO activity for julolidine‐POMs chromophores while keeping relatively good transparency window compared to similar purely organic systems.

Structural, Spectroscopic, Quantum Chemical, RDG, AIM, ELF, Fukui, O–H…N Hydrogen Bonding and NLO Activity of 2-Hydroxy-2-Phenyl Acetophenone Oxime: Experimental and Theoretical Approach

In the present work, organic 2-hydroxy-2-phenyl acetophenone oxime (2H2PAO) single crystal was synthesized and characterized by FT-IR, FT-Raman, UV-Vis, NMR spectra. The optimized geometrical parameters were computationally obtained at DFT/B3LYP level of theory. Harmonic vibrational frequencies were calculated and the spectral assignments have been done by potential energy distribution (PED) analysis using NCA method. The natural bond orbital (NBO), atoms in molecule (AIM) and Hirshfeld surface analysis and RDG were applied to evaluate the relative strength of hydrogen bond interactions and represent their effect on the stabilities of molecular arrangement. The chemical stability and NLO activity of title compound were evaluated by HOMO-LUMO analysis. MEP and Fukui function analysis recognizes the nucleophilic and electrophilic regions of the molecule and the chemical implication of molecule have been explained using ELF and LOL analysis. Photo-excitation of 2H2PAO has been examined to understand its light emitting behavior. Thermal stability of the grown crystal was examined by TG/DTA analysis to understand the withstanding temperature of 2H2PAO.

Oxalic acid incorporated acetamide single crystal growth dynamics, characterization, NLO and antimicrobial activities via shock wave treatment

Shock waves are applied to non-linear optical materials, particularly organic materials, due to their fast responsein electro-optic switchesand high nonlinearefficiency. At room temperature, an acetamide-doped oxalic acid single crystal has been grown using the slow evaporation method among other crystal growth techniques. Single crystal oxac applies to shock waves in steps of 50 and 100 shock waves to the tail or the material properties without altering the original crystal system. The grown and shock wave treated crystals of OXAC were structurally identified by X-ray diffraction and Fourier transform infrared spectroscopy,UV–Visible and Photoluminescence spectral analysis, nonlinear optical activity (NLO) studies. The antimicrobial studies such as antibacterial and antifungal activities of the grown crystals of oxalic acid, OXAC and OXAC with 50 and 100 shocks were performed and the obtained results were discussed. From we declared results, we state that the post shock wave induced OXAC crystal is enhancing properties of NLO, antimicroibial studies relatively pre shock wave induced OXAC crystal and reflected in structural and optical studies.

Synthesis, spectroscopic characterization and biological activities of some metal complexes with new heterocyclic azodye ligand 2-(2-hydroxynaphthalen-1-yl azo)-pyridin-3-ol

Metal complexes of [2-(2-hydroxynaphthalen-1-ylazo)-pyridin-3-ol] are derived from 2-amino-3-hydroxypyridine and β-naphthol was synthesized and characterized by thermal, spectral and analytical tools. The ligand was reacted with Mn(II), Fe(II), Co(II), Ni(II), Cu(II) and Zn(II) in 1:2 stoichiometry. The IR spectra confirms the azo ligand coordination to metal ions via azo nitrogen and phenolic oxygen of pyridine after deprotonation. Both IR and 1HNMR spectra recorded involvement of deprotonated hydroxyl groups with proton displacement. The magnified fluorescence was shown by Mn(II) and Ni(II) complexes. None of the prepared ligands or complexes show any NLO activity with KDP as standard. The DNA cleavage and anticancerous activities done. The influence of zinc chelates on cure characteristics of rubber compounds was estimated based on rheometer measurements. The ligand and metal complexes are tested in vitro against some bacteria and fungi species. The antioxidant activities, DNA cleavage and anticancerous activities done. Ligand and its complexes catalysed cleavage of DNA.

Molecular geometry, spectroscopic and NLO studies of 1-(chloromethyl)-4-fluorobenzene – A DFT study

The vibrational spectra of 1-(chloromethyl)-4-fluorobenzene have been studied in the 4000 - 400 cm -1 and 3500 - 50 cm -1 range, by FTIR and FT-Raman, respectively. In this work, structural analysis and vibrational frequencies are performed utilizing the GAUSSIAN 09W program with DFT/B3LYP strategy with basis set 6-311++G (d, p). Least differences are noted between the measured and scaled wavenumbers. The molecular vibrational assignments are confirmed by the PED (potential energy distribution) percentage. Frontier molecular orbital, natural bond orbital and Mullikan charge examinations are employed to explain the reason for intra and intermolecular charge exchange of the molecule. Reactive sites and chemical shifts are investigated by molecular electrostatic potential map and nuclear magnetic resonance analysis. Besides, the polarizability, the first hyperpolarizability, and total dipole moment of the molecule have been computed for describing its NLO activity.

Material synthesis, crystal growth, physico-chemical properties and second-order NLO activities of a novel L-histidinium phthalate potassium iodide (LHPPI) single crystal for NLO application

Material synthesis, crystal growth, physico-chemical properties and second-order NLO activities of a novel L-histidinium phthalate potassium iodide (LHPPI) single crystal for NLO application

2-thioxo -3N-(2-ethoxyphenyl) -5[4′-methyl -3′N-(2′-ethoxyphenyl) thiazol-2′(3′H)-ylidene] thiazolidin-4-one: Growth, spectroscopic behavior, single-crystal investigation, Hirshfeld surface analysis, DFT/TD-DFT computational studies and NLO evaluation

In this work, 2-thioxo -3 N-(2-ethoxyphenyl -5[4′-methyl -3′N-(2′-ethoxyphenyl) thiazol-2′(3′H)-ylidene] thiazolidin-4-one (E2Th2) was synthesized and its molecular structure determined by FT-IR, UV-Vis and NMR spectroscopic techniques along with a single crystal X-ray diffraction study. Quantum chemical calculations were performed to better understand its structural, spectroscopic and electronic properties such as HOMO and LUMO energy gap, MEP and global reactivity descriptors. Theoretical calculations were performed using density functional theory (DFT) based on the B3LYP/6-311G (d,p). Vibrational frequencies were assigned on the basis of PED and electronic transitions are calculated according to time-dependent density functional theory (TD-DFT). The HOMO and LUMO analysis are used to determine the charge transfer within the molecule. The NLO activity evaluation was based on the determination of the dipole moment, polarizability (α), first-order hyperpolarizability (β) and the second-order hyperpolarizability (γ) which were calculated using the same level of theory. The hyper-hardness descriptor (Γ) was explored and correlated with the NLO properties. Additionally, the stability of the molecule occurring from hyper-conjugative interaction, intramolecular hydrogen bond and charge delocalization were quantified using NBO analysis. The repulsive, attractive, and van der Waals strong and weak interactions were revealed by RDG and HS analyses. Finally, results have shown that the title compound can be used as attractive future NLO material.

Nonlinear optical activity of piperazine-1,4-diium bis(sulfanilate) compound

The present work investigates the NLO activity of the piperazine-1,4-diium bis(sulfanilate) molecule using density functionaltheory (DFT). The optimized molecular geometry and the vibrational wavenumber are calculated using DFT/B3LYP method with 6-311G (d,p) basis set.The possible hydrogen bonding interaction and charge delocalization are analyzed using natural bond orbital (NBO) analysis. Charge transfer interactionis identified using molecular electrostatic potential (MEP). Frontier molecular orbital (FMO) analysis illustrates that charge is transferred from sulfanilate anion and piperazinium cation. The electronic absorption transitions with different solvents are carried out by the time-dependent density functional theory (TD-DFT) method. The Fukui functional analysis is carried out to find the possible sites for the nucleophilic and electrophilic attack. The dipole moment (μ), mean polarizability (Δα), first order (β) and second order hyperpolarizability (γ) are calculated by DFT calculation. The NLO properties are relatively high when compared with urea, indicating the potential NLO application of PADSA.

From CsKTaF7 to CsNaTaF7 : Alkali Metal Cations Regulation to Generate SHG Activity.

Inorganic metal halides play important roles in wide range of areas including fluorescence, X-ray detection, and nonlinear-optics. Herein, two new mixed alkali metal tantalum fluorides, CsKTaF7 and CsNaTaF7 , have been obtained based on the strategy of cations regulation in A2 MF7 (A represents monovalent cations and M is d0 transition-metal cation) system by a conventional hydrothermal route. CsKTaF7 crystallizes in the centric Pnma space group, while CsNaTaF7 crystallizes in the polar Cmc21 space group and exhibits moderate and phase-matchable NLO activity. Both halides possess large optical band gaps above 5.0 eV. The crystal structure evolution, optical properties, and detailed theory calculations of these two halides were elucidated in this work.

Spectroscopic and Molecular Docking Studies of a Novel Biologically Active Heterocyclic Compound 2-Chloro-6-Methoxypyridine-4-Carboxylic Acid by Quantum Computational Method

The molecular structure, electronic and spectroscopic (FT-IR, FT-Raman, UV-Vis, 1H, and 13C NMR) behavior of the 2-chloro-6-methoxypyridine-4-carboxylic acid (CMPC) molecule was investigated. Quantum computational calculations for monomers and dimers of CMPC molecules were performed by the DFT method using the B3LYP/6-311++G (d,p) basis set. The title molecule displayed two types of dimers such as head to tail (HT) and head to head (HH). Fukui function and global softness of CMPC monomer and dimers were predicted through Mulliken population analysis. Natural Bonding Orbital analysis revealed the presence of intermolecular interaction between two monomer units. In non-linear optical property calculation, the monomer shows six times more than that of urea while the dimer displays thirty times greater than that of the urea molecule. Hence CMPC dimer shows better NLO activity than monomer. The MEP map identifies the reactive sites of the CMPC molecule. Lipinski’s rule of five and bioavailability score show that the CMPC molecule was a very good candidate for protein-ligand interaction and it may suitable for the new drug designing process. Finally, the molecular docking analysis shows an inhibition activity of CMPC molecule against antimicrobial activity and Mycobacterium tuberculosis.

Theoretical Study of the Structural, Optoelectronic, and Reactivity Properties of N-[5′-Methyl-3′-Isoxasolyl]-N-[(E)-1-(-2-)]Methylidene] Amine and Some of Its Fe2+, Co2+, Ni2+, Cu2+, and Zn2+ Complexes for OLED and OFET Applications

Herein, we report the structural, electronic, and charge transfer properties of N-[5′-methyl-3′-isoxasolyl]-N-[(E)-1-(-2-thiophene)] methylidene] amine (L) and its Fe2+, Co2+, Ni2+, Cu2+, and Zn2+ complexes (dubbed A, B, C, D, and E, respectively) using the density functional theory (DFT). All molecules investigated were optimized at the BP86/def2-TZVP/RI level of theory. Single point energy calculations were carried out at the M06-D3ZERO/def2-TZVP/RIJCOSX level of theory. Reorganization energies of the hole and electron (λh and λe) and the charge transfer mobilities of the electron and hole (μe and μh) have been computed and reported. The λe and λh values vary in the order D > E > A > B > C > L and E > A > D > L > C > B, respectively, while μe and μh vary in the order B > C > L > A > E > D and C > B > A > L > E > D, respectively. μh of B (39.5401 cm2·V−1S−1) and C (366.4740 cm2·V−1s−1) is remarkably large, suggesting their application in organic light-emitting diode (OLED) and organic field-effect transistor (OFET) technologies. Electron excitation analysis based on time-dependent (TD)-DFT calculations revealed that charge transfer excitations may significantly affect charge transfer mobilities. Based on charge transfer mobility results, B and C are outstanding and are promising molecules for the manufacture of electron and hole-transport precursor materials for the construction of OLED and OFET devices as compared to L. The results also show that L and all its complexes interestingly have higher third-order NLO activity than those of para-nitroaniline, a prototypical NLO molecule.

The effect of the additional phenyl moiety on the linear and quadratic nonlinear optical properties of chromophores with vinyl-quinoxalinone-vinyl π-bridge

Four novel push-pull tricyanofuran-based chromophores with vinylene-quinoxalinone-vinylene π-conjugated bridge and aniline type donor with phenyl moiety either introduced into the donor/acceptor as substituent or fused with aniline in carbazole and phenothiazine structures have been synthesized and their linear and nonlinear optical properties were systematically investigated by UV–Vis spectroscopy and DFT calculations. Addition of benzene ring as substituent to the chromophore leads to moderate (22–36 pm/V) macroscopic NLO activity of composite chromophore/PMMA materials, while guest-host polymers doped with chromophores with fused heterocyclic donor moiety demonstrate higher d33 values up to 47 pm/V. Chromophore-containing polymer films preserve more than 90% of d33 after 1000 h at ambient temperature.

Investigation of physicochemical properties, photoluminescence, laser damage threshold, antimicrobial, NLO activity of L-proline manganese chloride monohydrate for optoelectronic applications

Investigation of physicochemical properties, photoluminescence, laser damage threshold, antimicrobial, NLO activity of L-proline manganese chloride monohydrate for optoelectronic applications

Synthesis, structure, NBO, Hirshfeld surface, NMR, HOMO-LUMO, UV, photoluminescence, z scan, vibrational and thermal analysis of piperazinedi-ium tetrakis (μ2‑chloro)-diaqua-dichloro-di-cadmium single crystal

Single crystals of Piperazinedi-ium tetrakis (μ2‑chloro)-diaqua-dichloro-di-cadmium(ii), a three-dimensional framework of chained chlorocadmate with the organic piperazine as a template, are synthesized by slow evaporation and confirmed by single-crystal X-ray diffraction. Theoretical analysis such as geometrical optimization, NBO, Hirshfeld surface, hyperpolarizability and Frontier molecular orbitals analyzes were performed using DFT calculations. The most stable molecular structure is optimized by DFT/ B3LYP method with the LAN2DZ basis set in the Gaussian 09 program package. The intra and intermolecular interactions and donor-acceptor energy relations are studied using the NBO 5.0 program. The analysis reveals that the strength of hydrogen-bonded intermolecular interaction is in the order NH…O> NH…Cl > CH…Cl. The NMR, UV-Visible, FTIR and FT-Raman spectra are recorded and analyzed for confirmation of electronic structure and intermolecular interactions. The simulated FTIR and FT-Raman spectra are matched with the experimental spectra. The vibrational wavenumbers are calculated and assigned on the basis of potential energy distribution using MOLVIB software. The hydrogen-bonded intermolecular interactions such as NH…Cl, OH…Cl, CH…Cl and charge delocalization give stability to the dimer structure. The 2D fingerprint maps revealed that the highest share of total Hirshfeld surface is attributed to H….Cl/Cl…H interactions with 62.5%. The charge transfer from the metal atom to the amine group and the low HOMO-LUMO energy gap (3.8469 eV) enhance the NLO activity of the molecule. The open and closed aperture Z-scan technique revealed that the title compound has the highest nonlinear absorption coefficient value β(4.118 × 10−4 m/W) with a greater third-order nonlinear optical response than the five other optical limiters we have studied. TGA and DTA reveal the suitability of the crystal for NLO and other laser applications up to 92.37 °C. The results of the present investigation predict that the crystal is a stable complex with a high nonlinear optical property that can be used as a new violet-light emitting material and as an efficient optical limiter.

Molecular Structure, Experimental and Theoretical Vibrational Spectroscopy, (HOMO-LUMO, NBO) Investigation, (RDG, AIM) Analysis, (MEP, NLO) Study and Molecular Docking of Ethyl-2-{[4-Ethyl-5-(Quinolin-8-yloxyMethyl)-4H-1,2,4-Triazol-3-yl] Sulfanyl} Acetate

The spectroscopic characterization of the new synthesized heterocyclic aromatic organic compound ethyl −2-{[4-ethyl −5-(quinolin- 8-yloxymethyl) -4H- 1,2,4-triazol −3-yl] sulfanyl} acetate (abbreviated by Q-tsa) was carried out using experimental FTIR, UV–Vis, 1H, and 13C NMR techniques. To support the analytical results, theoretical calculations were performed on Q-tsa using DFT method associated with B3LYP functional with 6-31G(d,p) and 6-311G(d,p) basis sets. Furthermore, the reactivity of the title compound was studied by the investigation of frontier molecular orbitals (FMO) analysis, HOMO-LUMO energies, density of state (DOS), molecular electrostatic potential (MEP), global and local chemical reactivity descriptors. Thermodynamic properties were separately computed and discussed. The attractive, repulsive and van der Waals strong and weak interactions in Q-tsa were performed via RDG analysis followed by the investigation of topological properties via AIM theory. Similarly, the NLO activity of the studied compound was highlighted by computing the first hyperpolarizability in different available solvents. Finally, through molecular docking, the biological activity of Q-tsa was studied and discussed.

HgBrI: a possible tecton for NLO molecular materials?

Mixed mercury(II) halogenides have been known for a long time as good NLO (non-linear optic) materials. The NLO properties are due to the halogen disposition in the solid state and the electron distribution among the bonds formed by soft elements. We investigated the possibility of using HgBrI as a asymmetric tecton in the preparation of noncentrosymmetric crystalline compounds, by exploiting the coordinating power of Hg(II) toward N-donor ligands, and seven coordination complexes have been obtained. To unravel the nature of these complex systems we combined the data from different techniques: Raman spectroscopy, SC-XRD and Second Harmonic Generation, supported by a periodic DFT computational approach. In HgBrI crystalline products with low symmetry, the presence of substitutional disorder leads to a lack of the inversion center conferring NLO activity, which is absent in analogous complexes of Hg(II) halogenides. These results indicate HgBrI as an interesting tecton to obtain metallorganic NLO materials.

Synthesis, photophysical and nonlinear optical properties of push-pull tetrazoles.

A 2,5-disubstituted tetrazole with p-nitrophenyl and 3-pyridyl units as acceptors (1a), and three push–pull tetrazoles with p-nitrophenyl as an acceptor and phenyl (1b), 2-(dibenzo[b,d]furan-4-yl) (1c), and 4-(N,N-diphenylamino)phenyl (1d) as donor groups, were synthesized by copper-catalyzed aerobic C–N coupling of p-nitrophenyl tetrazole with appropriately substituted aryl boronic acids. The absorption and emission spectra of 1a–c showed minimal dependence on the polarity of the solvent; however, in the case of 1d a blue shift was noted in the longest absorption band (λ1) as the polarity increased. The fluorescence intensity of the title compounds was found to be solvent-dependent; however, no apparent correlation to solvent polarity could be established. The absorption and emission characteristics of 1a–d were also influenced by the nature of the substituent as 1d, bearing a strong electron donating 4-(N,N-diphenylamino)phenyl group, displayed a significant red shifted absorption (λ1) as well as emission (λem) bands compared to other compounds. Time dependent density functional calculations (CAM-B3LYP/6-311++G**) revealed that the longest wavelength band (λ1) is associated with an intramolecular charge transfer (ICT) from HOMO/HOMO-1/HOMO-2 → LUMO/LUMO+1 in these molecules. The first hyperpolarizability values, βHRS, of 1a–d were measured using the solution-based hyper-Rayleigh scattering technique using a femtosecond Ti:Sapphire laser and the highest NLO activity was measured for 1d with the greatest push–pull characteristics. A strong correlation was observed between the calculated hyperpolarizability (βtot) and experimentally measured values (βHRS).

Spectroscopic and quantum chemical computation on molecular structure, AIM, ELF, RDG, NCI, and NLO activity of 4-VINYL benzoic acid: A DFT approach

Vibrational spectral analysis was carried out for 4-Vinyl Benzoic acid (4VBA) by using Fourier transform infrared (FT-IR) and FT-Raman spectroscopy in the range of 400–4000 and 50–3500 cm−1 respectively. The optimized geometrical parameters were computationally obtained at the DFT/B3LYP level of theory. 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. 13C and 1H NMR spectra were recorded and 13C and 1H nuclear magnetic resonance chemical shifts of the molecule were calculated using the gauge independent atomic orbital (GIAO) 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.

A ‘donor-free’ chromophore with a silicon-based acceptor group for second order nonlinear optics

In this paper we report an investigation on the linear and nonlinear properties of a non-classic push-pull molecule, based on the molecular design concept of a ‘donor-free’ chromophore. Herein a terthiophene unit acts both as a donor and a π-spacer group and a tris(trimethylsiloxy)silane substituent as an acceptor group. This latter can represent a model of a fragment of silica surface and it has been compared with a classic acceptor unit like the nitro group. The ‘donor-free’ chromophores have also been compared to more typical push-pull chromophores by replacing the terthiophene unit with the N,N-dimethylamino donor group.Despite the silane group only slightly impacts on the electronic and linear properties of the terthiophene, our results reveal high μβEFISH values for silane-functionalized derivatives producing a NLO activity stronger than that of the nitro substituted. Finally, the investigated ‘donor-free’ NLO-phore exhibits interesting physical properties relevant in term of nonlinearity/transparency trade-off, a highly desired requirement for second-order NLO materials.