Nonlinear Optical Properties Of Compounds Research Articles

Exploring the functional properties of Trimethoxy-Phenylpyridine as efficient optical and nonlinear optical material: A quantum chemical approach

In the current study, the 2,6-diphenyl-4-(3,4,5-trimethoxyphenyl)pyridine (compound 1) has been investigated as proficient material for optoelectronic and nonlinear optical (NLO) applications. In order to highlight the potential at both solid-state (bulk) and molecular levels, different electronic and optical parameters were investigated. The optical and electronic parameters such as refractive index, reflectivity, dielectric function, extinction coefficient, conductivity, electronic band structure, density of states (DOS) of newly reported trimethoxy-phenylpyridine at bulk (solid-state) level have been studied. The band gap is found to be 2.817 eV, which revealed the photon absorption competency has been improved in compound 1 due to narrow band gap and has the capability of containing the absorbed energy. Other calculated optoelectronic properties also revealed that the compound 1 might be better for semiconductor applications. Additionally, the geometric parameters, polarizability (isotropic and anisotropic) and third-order NLO polarizability have been computed at molecular level. For compound 1, its isotropic and anisotropic values are found to be 63.41 × 10−24 esu and 46.22 × 10−24 esu, respectively. The calculated γ amplitude for studied material has been computed as 187.53 × 10−36 esu that is about 25 times bigger than that of the γ amplitude for pNA (a prototype NLO molecule). The third order NLO response for compound 1 has been further tuned through the designing of its further derivatives in the form of compounds 1a, 1b and 1c. Thus, the present study highlights the important optoelectronic and NLO properties of compound 1 and its derivatives.

5-Phenyl thiophene amino phenol derivatives: Synthesis, spectroscopic characterization, computational study and antimicrobial activity

(((5-phenylthiophen-2-yl) methylene) amino) phenol derivatives were synthezised and characterized by IR and NMR. The density functional theory (DFT) method with 6–311++G (d,p) basis set was used for both calculations of molecular geometries and spectroscopic parameters. Frontier molecular orbitals and molecular electrostatic potential maps for compounds 1a, 1b and 1c were obtained. Due to the differences observed in the theoretical spectral parameters, NH⋯O type intermolecular/intramolecular hydrogen bonds in the molecular structures of compounds were proposed. To determine the nonlinear optical properties of compounds, the mean polarizability (α) and the first hyperpolarizability (β) obtained as 44.2388 × 10−24 esu and 373.1267 × 10−31 esu for compound 1a, 43.8141 × 10−24 esu and 195.2893 × 10−31 esu for compound 1b, 36.9489 × 10−24 esu and 120.73825 × 10−31 esu for compound 1c, respectively were used. These values indicate that compounds can be suggested as a good nonlinear optical material. In addition, the antimicrobial properties of compounds were investigated by considering antileishmanial and antibacterial activities. The compounds were evaluated against Leishmania infantum promastigots for antileishmanial activity and against five standard bacteria (Escherichia coli, Shigella flexneri, Yersinia enterocolitica, Salmonella typhimurium and Salmonella enterica) for antibacterial activity, by microdilution broth assay with Alamar Blue Dye. Results show that only compound 1a has high antileishmanial activity and can be evaluated in leishmaniasis treatment after in vivo studies and also considered in pharmacological studies for antibacterial activity.

Impact of ligand rotation: Synthesis, crystal structures and third-order nonlinear optical properties of Mn(II), Cu(II) and Ni(II) complexes with 5‑diethylamino‑2‑((4‑(phenyldiazenyl) phenylimino) methyl) phenol

Three new coordination compounds containing 5‑diethylamino‑2‑((4‑(phenyldiazenyl) phenylimino) methyl) phenol ligand have been synthesized and fully characterized. Single crystal structure showed that the ligand shows multiple coordination mode and the phenyl group next to azo group could rotate during the coordination process. In Mn(HDAPPP)2Cl2·CH3CN (1), the HDAPPP behaved as a mono ligand because of the N of the imine group is protonated in the keto form and does not participate in coordination. While the Cu(DAPPP)2 (2) and Ni(DAPPP)2 (3) are classic complexes containing azo-Schiff base ligand. The fluorescence emission peaks of compounds indicated that the fluorescence of the compounds are mainly derived from the π-π* charge transition of the ligand and affected by the rotation of ligand. The UV–Vis data revealed that the compound 1–3 with the maximum absorption peak at 425 nm, 440 nm and 338 nm, respectively. This clearly confirmed that the compound 1 is mainly based on the keto configuration while the compound 3 is mainly based on the enol configuration. Z-scan experiments showed that all compounds exhibited reverse saturable absorption effect and self-defocusing effect for nonlinear optical materials. The nonlinear absorption coefficients (β) of compound 1–3 are evaluated to be 6 × 10−11 m·W−1, 4.4 × 10−11 m·W−1, and 1.7 × 10−11 m·W−1 respectively, and the nonlinear refraction coefficients (n2) are −1.4 × 10−17 m2·W−1, −1.6 × 10−17 m2·W−1, −7.0 × 10−18 m2·W−1 respectively. The nonlinear optical property of compound 1 and 2 are better than compound 3, which are influenced by ligand rotation after coordination.

Spectroscopic characterization and density functional studies of new thiadiazole 1,1-dioxide compounds

New thiadiazole compounds, 3-imino-4-(anthracene-9-yl)-1,2,5-thiadiazolidine 1,1-dioxide (I) and 3-imino-4-(10-chloroanthracene-9-yl)-1,2,5-thiadiazolidine 1,1-dioxide (II) were synthesized and characterized by Fourier Transform Infrared Spectroscopy (FTIR), 13C and 1H NMR and UV–vis spectroscopic methods. Calculations of molecular geometries and spectroscopic parameters were performed using DFT/6–311++G(d,p) method. Frontier Molecular Orbitals (FMOs), Non-Linear Optical (NLO) properties and Molecular Electrostatic Potential (MEP) maps of newly synthesised compounds were obtained. The some considerable differences between experimental and calculated vibrational frequencies and NMR chemical shift values can be attributed to the presence of NH⋯O type intermolecular hydrogen bonds in the molecular structures of both compounds. NLO properties of compounds were determined by using the mean polarizability (α) and the first-order hyperpolarizability (β) values calculated as 36.8326 × 10−24/18.7571 × 10−31 esu for I, 36.9489 × 10−24/31.6544 × 10−31 esu for II, respectively at the mentioned computational level. These values are greater than the ones of urea (α = 4.9067 × 10−24 and β = 7.8782 × 10−31 esu) and therefore, NLO properties study demonstrates that the both compounds, especially compound II, can be suggested as a good nonlinear optical material.

A combined experimental and computational study of 3-bromo-5-(2,5-difluorophenyl) pyridine and 3,5-bis(naphthalen-1-yl)pyridine: Insight into the synthesis, spectroscopic, single crystal XRD, electronic, nonlinear optical and biological properties

Carbon-carbon coupling play a vital role in the synthetic field of organic chemistry. Two novel pyridine derivatives: 3-bromo-5-(2,5-difluorophenyl)pyridine (1) and 3,5-bis(naphthalen-1-yl)pyridine (2) were synthesized via carbon-carbon coupling, characterized by XRD, spectroscopic techniques and also investigated by using density functional theory (DFT). XRD data and optimized DFT studies are found to be in good correspondence with each other. The UV–Vis analysis of compounds under study i.e. (1) and (2) was obtained by using “TD-DFT/B3LYP/6-311 + G(d,p)” level of theory to explain the vertical transitions. Calculated FT-IR and UV–Vis results are found to be in good agreement with experimental FT-IR and UV–Vis findings. Natural bond orbital (NBO) study was performed using B3LYP/6-311 + G(d,p) level to find the most stable molecular structure of the compounds. Frontier molecular orbital (FMO) analysis were performed at B3LYP/6-311 + G(d,p) level of theory, which indicates that the molecules might be bioactive. Moreover, the bioactivity of compounds (1) and (2) have been confirmed by the experimental activity in terms of zones of inhibition against bacteria and fungus. Chemical reactivity of compounds (1) and (2) was indicated by mapping molecular electrostatic potential (MEP) over the entire stabilized geometries of the compounds under study. The nonlinear optical properties were computed with B3LYP/6-311 + G(d,p) level of theory which are found greater than the value of urea due to conjugation effect. Two state model has been further employed to explain the nonlinear optical properties of compounds under investigation.

Enhancement of nonlinear optical properties of compounds of silica glass and metallic nanoparticle

The aim of this paper is to introduce a method for enhancing the nonlinear optical properties in silica glass by using metallic nanoparticles. First, the T-matrix method is developed to calculate the effective dielectric constant for the compound of silica glass and metallic nanoparticles, both of which possess nonlinear dielectric constants. In the second step, the Maxwell–Garnett theory is exploited to replace the spherical nanoparticles with cylindrical and ellipsoidal ones, facilitating the calculation of the third-order nonlinear effective susceptibility for a degenerate four-wave mixing case. The results are followed by numerical computations for silver, copper and gold nanoparticles. It is shown, graphically, that the maximum and minimum of the real part of the reflection coefficient for nanoparticles of silver occurs in smaller wavelengths compared to that of copper and gold. Further, it is found that spherical nanoparticles exhibit greater figure-of-merit compared to those with cylindrical or ellipsoidal geometries.

The effect of heterocyclic π bridges on second order nonlinear optical properties of compounds formed between ferrocenyl and corannulenyl

Among D–π–A type compounds, when imidazole acts as a π bridge (endo/exo-3), the βtot values are almost 2 times as large as when the phenyl acts as a π bridge (endo/exo-2).

On the vibrational linear and nonlinear optical properties of compounds involving noble gas atoms: HXeOXeH, HXeOXeF, and FXeOXeF

The vibrational (hyper)polarizabilities of some selected Xe derivatives are studied in the context of Bishop-Kirtman perturbation theory (BKPT) and numerical finite field methodology. It was found that for this set of rare gas compounds, the static vibrational properties are quite large, in comparison to the corresponding electronic ones, especially those of the second hyperpolarizability. This also holds for the dc-Pockels β(-ω;ω,0), Kerr γ(-ω;ω,0,0) and electric field second harmonic generation γ (-2ω;ω,ω,0) effects, although the computed nuclear relaxation (nr) vibrational contributions are smaller in magnitude than the static ones. HXeOXeH was used to study the effects of electron correlation, basis set, and geometry. Geometry effects were found to lead to noticeable changes of the vibrational and electronic second hyperpolarizability. A limited study of the effect of Xe insertion to the nr vibrational properties is also reported. Assessment of the results revealed that Xe insertion has a remarkable effect on the nr (hyper)polarizabilities. In terms of the BKPT, this is associated with a remarkable increase of the electrical and mechanical anharmonicity terms. The latter is consistent with the anharmonic character of several vibrational modes reported for rare gas compounds.

Synthesis of methyl 12-aryl-9,9-dimethyl-11-oxo-7,8,9,10,11,12-hexahydrobenzo[a]acridine-10-carboxylate

A three-component condensation of 2-naphthylamine, aromatic aldehydes, and methyl 2,2-dimethyl-4,6-dioxocyclohexanecarboxylate afforded methyl (cis,trans)-12-aryl-9,9-dimethyl-11-oxo-7,8,9,10,11,12-hexahydrobenzo[a]acridine-10-carboxylates. Spectral luminescence and nonlinear optical properties of compounds obtained were investigated.

Syntheses, Crystal Structures, and Optical Properties of Metal Complexes with 4′,5′‐Diaza‐9′‐(4,5‐disubstituted‐1,3‐dithiol‐2‐ylidene)fluorene Ligands

AbstractFour complexes with 4′,5′‐diaza‐9′‐[4,5‐bis(methylthio)‐1,3‐dithiol‐2‐ylidene]fluorene (L1) or 4′,5′‐diaza‐9′‐[4,5‐bis(ethylthio)‐1,3‐dithiol‐2‐ylidene]fluorene (L2) were synthesized. The complexes [Co(L1)2Cl2]·2CH3OH (1), [Cu(L2)2Cl2]·CH3OH·0.5CH2Cl2 (3), and [Cu(L2)2Br2]·CH3OH (4) adopt a trans configuration and the compound [Cd(L1)2(NO3)2] (2) is a cis structure. Short S···S, C···C, and C···S contacts were found to be important in the molecular packing. Both the solution and solid‐state electronic spectra show a redshift in the intramolecular CT bands when forming metal complexes. This intramolecular charge transition in the solid state is enhanced relative to that in solution. Their third‐order nonlinear optical properties of compounds 1–4 were studied, and the results reveal that these complexes exhibit negative γ values (about 10–30) and are self‐defocusing samples. These γ values are comparable to those of the known cluster compounds. The trans coordination of the two ligands to the metal center would be beneficial to the NLO properties. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)

Syntheses, Structures, and Nonlinear Optical Properties of Heteroselenometallic W−Se−Ag Cluster Compounds Containing Phosphine Ligands

Treatment of [Et4N]2[WSe4] with a 1:1 mixture of AgNO3 and PCy3 (Cy = cyclohexyl) in the absence of iodide afforded a linear trinuclear compound [(mu-WSe4)(AgPCy3)2] (1). A similar reaction in the presence of iodide gave rise to the isolation of the cubanelike compound [(mu3-WSe4)Ag3(PCy3)3(mu3-I)] (2). Treatment of [Et4N]2[WSe4] with AgI in the presence of bidentate phosphine ligands bis(diphenylphosphino)amine (dppa) and bis(diphenylphosphino)methane (dppm) afforded the tetranuclear compounds [(mu3-WSe4)Ag3(mu-I)(mu-dppa)2] (3) and [(mu3-WSe4)Ag3(mu3-I)(mu-dppm)2] (4), respectively, which exhibit an open butterfly configuration. A novel hexanuclear cluster compound [(mu3-WSe4)2Ag4(mu-dppm)3] (5) was obtained from interaction of [Et4N]2[WSe4] with AgNO3 and dppm in the absence of iodide source. The above cluster compounds are electrically neutral and air-stable in both solution and the solid state and have been characterized by electronic, infrared, mass, and NMR spectroscopies. The solid-state structures of five cluster compounds have been established by X-ray crystallography. The nonlinear optical properties of compounds 4 and 5 were examined by z-scan techniques with 7 ns pulses at 532 nm. The optical limiting effects of compounds 1, 2, 4, and 5 were determined and compared with related argentoselenometallic compounds.

Syntheses, characterization and optical properties of some copper(i) halides with 1,10-phenanthroline ligand

The hydrothermal reactions of CuX2 or CuX with phen (1,10-phenanthroline) have resulted in the syntheses of eight compounds 1–8. In these, 1∶1 adducts of CuX/phen are reported: ionic [Cu(phen)2][CuX2] (X = Cl 1, Br 2) and dimer [Cu2I2(phen)] 3; the trinuclear clusters [Cu3X3(phen)2] (X = Br 5, I 7) were first prepared and the structures can be best described as 1∶1 adducts of dimers and CuX; the chain compounds 6 and 8 belong to the same series with the formula [CuX2L] (L = organic ligand), but the chain arrangement is different; the structure of 4 is yet being refined. Compounds 1–8 have a high thermal stability. The third-order nonlinear optical properties of compounds 5, 6 and 8 were investigated and all exhibit a reverse saturable absorption (α2 > 0) and self-defocusing performance (n2 < 0).

Hydrothermal synthesis, crystal structure and third-order non-linear optical property of a novel one-dimensional copper(I) cyanide–organodiimine coordination polymer [Cu 6(CN) 6(phen) 4] n (phen=1,10-phenanthroline)

A novel one-dimensional chain coordination polymer [Cu 6(CN) 6(phen) 4] n 1 was synthesized from the simple hydrothermal reaction of Cu(CH 3COO) 2·H 2O, K 3[Fe(CN) 6] and phen·H 2O. With phen, CuCN exhibits a novel B–C–B–C chain array, namely the infinite chain is propagated via alternately three-coordinate (B) and four-coordinate (C) sites of monovalent Cu ions. It should also be noticed that the compound is the first example where the parent chain not only exhibits the [Cu(phen)] + side arm, but also is directly bound to the chelate ligand. Moreover, the third-order non-linear optical property of compound 1 was also investigated and it shows the reverse saturable absorption and self-focusing performance.

Hydrothermal synthesis, crystal structure and third-order non-linear optical property of a novel three-dimensional supramolecular network compound [Ni(IN) 2(H 2O) 4] (IN=isonicotinate)

A three-dimensional supramolecular compound [Ni(IN) 2(H 2O) 4] 1 has been rationally designed and synthesized by hydrothermal method, and the structure was characterized with elemental analysis, FT–IR spectrum and X-ray diffractometer. In the packing structure, the stronger intermolecular O–H⋯O hydrogen-bonded and π–π stacking interactions are the most significant factors of controlling the novel supramolecular sheet fashion for the title compound. The third-order non-linear optical property of compound 1 was also investigated, and it exhibits nicer reverse saturable absorption and self-focusing performance.

Solid-state syntheses of M–Cu–S (M=Mo and W) clusters, crystal structure and non-linear optical properties of {MS 4[Cu( p-MeOC 6H 4) 3P] 2}·0.5C 6H 12

The title compounds {MS 4[Cu( p-MeOC 6H 4) 3P] 2}·0.5C 6H 12 [M=Mo ( 1) or W ( 2)] were synthesized for non-linear optical studies by a solid state reaction of (NH 4) 2MS 4, CuI and ( p-MeOC 6H 4) 3P. A single crystal X-ray analysis reveals that 1 possesses a linear skeleton with a Mo center slightly distorted from tetrahedron and two Cu centers distorted from trigonal planar. The non-linear optical properties of 1 were investigated by the Z-scan and picosecond time-resolved pump-probe measurements at 532 nm. The results obtained revealed that thermally induced non-linear effect was dominant in the nanosecond time-scale while stimulated Rayleigh-wing scattering was observed in the picosecond measurement. Its non-linear refractive index was determined to be −3.52×10 −17 m 2 W −1 for nanosecond time-scale and 4.32×10 −19 m 2 W −1. Nonlinear optical properties of compound 2 were investigated at same condition similar to 1, no non-linear optical behavior was observed for 2, although it might have a similar structure to that of compound 1.

Influence of Metal Complexing on the Nonlinear-Optical Properties of Compounds with High Molecular Symmetry

Coordination bonding of 1,5-diphenylpentadienone was studied with the aim to prepare compounds exhibiting third-order nonlinear optical properties. The volume resistivity of these compounds was studied as influenced by the third-order nonlinear susceptibility tensor.

Synthesis, crystal structure and large third-order nonlinear optical properties of two novel nest-shaped clusters [MOS3Cu3(SCN)(Py)5] (M=Mo, W)

Two new candidates for nonlinear optical (NLO) materials, [MoOS3Cu3(SCN)(Py)5] (1) and [WOS3Cu3(SCN)(Py)5] (2), were synthesized. They show nest-shaped skeletal structure. The crystal structure of compound (1) was characterized by X-ray diffraction. The NLO properties of 1 and 2 were determined through the Z-scan technique. [MoOS3Cu3(SCN)(Py)5] exhibits both very strong NLO absorption and a self-defocusing effect, α2=4.8×10-10 m W-1 and n2=-6.8×10-17 W-1 in a 2.0×10-5 mol dm-3 acetonitrile solution. NLO properties of compound [WOS3Cu3(SCN)(Py)5] are similar to those of [MoOS3Cu3(SCN)(Py)5], strong NLO absorption and self-defocusing effect, α2=6×10-11 m W-1 and n2=-1.2×10-17 W-1, when measured in a 1.9×10-5 mol dm-3 DMF solution. Their hyperpolarizability γ values were calculated to be 5.8×10-27 esu for cluster 1 and 2.2×10-27 esu for cluster 2, respectively. The large γ value should define clusters 1 and 2 as very promising candidates for NLO materials.