Third order nonlinear optical properties of ethyltriphenylphosphonium bis(2-thioxo-1,3-dithiole-4,5-dithiolato)aurate (III)

A novel organometallic compound, ethyltriphenylphosphonium bis(2-thioxo-1,3-dithiole-4,5-dithiolato)aurate (III), abbreviated as TPEPADT, was synthesized. The TPEPADT doped poly(methyl methacrylate) (PMMA) thin film with a mass fraction of 1% (1 wt.%) was prepared by using a spin-coating method. The third-order nonlinear optical properties of TPEPADT in acetonitrile solution and TPEPADT-doped PMMA thin film were investigated by using the laser Z-scan technique at the wavelength 1064 nm with laser duration of 20 ps. The linear refractive index of the polymer thin film was also studied. The Z-scan curves revealed that both TPEPADT in acetonitrile solution and the polymer thin film possessed negative nonlinear refraction, exhibiting a self-defocusing effect and nonlinear absorption was negligible under the experimental conditions used. The nonlinear refractive index was calculated to be ?1.9 × 10^?18 m²/W for TPEPADT in acetonitrile solution and ?8.9 × 10^?15 m²/W for the polymer thin film. These results suggest that TPEPADT have potential for the application of all-optical switching devices.     

Peculiarities of crystal structures and magnetic properties of Cu(II) and Ni(II) mixed-ligand complexes on the 1,3-dithiole-2-thione-4,5-dithiolate basis

Mixed-ligand Cu(II) and Ni(II) complexes, [Cu(dmit)(bpy)]₂ (I), [Ni(dmit)(phen)₂] (II) and [Ni(dmit)(phen)₂]·CH₂Cl₂ (III) (dmit=1.3-dithiole-2-thione-4.5-dithiolate, phen=1.10-phenantroline, bpy=2.2′-bipyridine) have been prepared by ligand exchange between phen or bpy and (Bu₄N)₂[M(dmit)₂] (M=Ni, Cu) and characterized by elemental analysis, IR spectroscopy, single-crystal X-ray analysis and by investigation of magnetic and resonance properties. In complex I, the monomeric units form dimers in a head-to-tail arrangement by weak coordination bonds between copper and dithiolate sulfur atoms and π–π interactions between dmit and bpy from neighboring monomers. Dimers in I are further extended into chains by weak Cu–S(thione) contacts. In crystal packing of complex II and III, there exists a weak π–π interaction between two parallel phen molecules of the adjacent complexes. As a consequence, the magnetic and resonance characteristics of copper complex may be described in approximation of exchange-coupled pairs of Cu²⁺ ions with ion spin S=1/2. The nickel complexes are described by isotropic exchange model for single-site spin S=1.     

Preparation, spectrographic characterization, thermal, second and third order nonlinear optical properties of 4,5-bis(foroylsulfanyl)-1,3-dithiole-2-thione

A novel nonlinear optical organic crystal, 4,5-bis(foroylsulfanyl)-1,3-dithiole-2-thione (BFDT), was prepared and characterized by elemental analyses, infrared and Raman and X-ray powder diffraction spectroscopy, thermal analysis, specific heat, optical transmission and second harmonic generation determinations. It exhibits powder second harmonic efficiencies about 1.3 times that of urea. The transparent region is from 442 to 3200 nm. The BFDT doped PMMA composite films were fabricated by means of spin-coating. The third order nonlinear optical properties of the films were investigated by using the Z-scan technique at 532 nm with 20 ps. They exhibited very large self-defocusing effects and negligible nonlinear absorption.     

Growth, optical, dielectric and ESR studies on tetrathiourea mercury(II) tetrathiocyanato manganate(II): An organometallic complex NLO crystal

Single crystals of tetrathiourea mercury(II) tetrathiocyanato manganate(II); Hg(N₂H₄CS)₄Mn(SCN)₄, (TMTM) were grown by slow solvent evaporation technique. The grown crystals were confirmed by single crystal and powder X-ray diffraction analysis. The optical absorption spectrum of TMTM in a mixed solvent of acetone and water shows the near ultra-violet cut-off wavelength corresponding to the absorption maximum as 335 nm. FT-IR spectrum identifies the characteristic absorption bands of thiourea and thiocyanate in both middle and far infrared regions, which further confirm the incorporation of both the ligands in the resulting compound. The electron spin resonance spectrum of TMTM was recorded both at room temperature and −196 °C, which reveals that the Mn environment is symmetrical with respect to the NCS ligand distribution. It is also interesting to note that there is no hyperfine coupling between Mn nucleus and its free electrons at both room temperature and −196 °C. The dielectric constant as well as dielectric loss of the sample were calculated for varying frequencies under different temperatures.     

Determination of optical nonlinearities in Cu(mpo)2 by Z-scan technique

The optical nonlinearities of Cu(mpo)₂ [formula = C₁₀H₈N₂CuO₂S₂] complex have firstly been investigated by using the Z-scan technique with a nanosecond-pulsed Nd:YAG laser at its second harmonic (532 nm) radiation. The nonlinear optical absorption and refraction coefficients of Cu(mpo)₂ have been measured with the different on-axial peak irradiances I ₀ at the waist ranging from 0.48 to 5.66 GW/cm². The nonlinear transmittance characteristics exhibit the near resonant two-photon absorption (TPA) at 532 nm and are explained by a population redistribution model. The nonlinear absorption originates from the near resonant TPA while the mechanism of the nonlinear refraction is the near resonant TPA transition enhancement. The linear increasing dependences of the optical nonlinearities on the incident irradiance arise from the population redistribution due to the near resonant TPA.     

In situ formation of bis(8-hydroxyquinoline) zinc(II) complex in the interlayer spaces of smectites by solid–solid reactions

Bis(8-hydroxyquinoline) zinc(II) complex (Znq₂), an electroluminescent material used for organic light emitting devices (OLEDS), formed in the interlayer spaces of smectites by solid–solid reactions between Zn(II)-smectites (Zn(II)-synthetic saponite and Zn(II)-montmorillonite) and 8-hydroxyquinoline at ambient condition. The intercalation of 8-hydroxyquinoline molecules into Zn(II)-smectites and the in situ complex formation of Znq₂ chelate in smectites were confirmed by powder XRD, FT-IR, TG–DTA, UV–vis absorption and photoluminescence spectroscopies, and elemental (CHN) analysis. The photoluminescence intensity of the Znq₂ complex in synthetic saponite was higher than that of the complex in montmorillonite, suggesting the very low content of quenching impurities in synthetic saponite. The difference in the luminescence bands were thought to be caused by the different molecular structure and molecular packing of the complex formed in the interlayer spaces.     

Investigation on third-order nonlinear optical properties of two Au(dmit)2/PMMA thin films by Z-scan technique in picosecond pulse regime

The third-order nonlinear optical properties of two Au(dmit)₂/PMMA compound thin films, hexadecyltrimethylammonium bis(1,3-dithiole-2-thione-4,5-dithiolato)aurate and tetramethylammonium bis(1,3-dithiole-2-thione-4,5-dithiolato)aurate (abbreviated as MeAu and CtAu, respectively) with a doping concentration of 1?wt.% deposited on quartz-glass substrate were characterized by a single beam Z-scan technique at 1064?nm with 20?ps laser pulse width and 10?Hz repetition rate. The dominant nonlinear refraction and tiny nonlinear absorption of both materials lead to a larger possibility for them to be applied as promising candidates of all-optical switching. The results of two figures of merit, |W|?1 and |T|?1, were also calculated; this further validated the excellent properties of the materials for applications of the nonlinear optics.     

Propagation of light in(2+1)-dimensional nonlinear optical media with spatially inhomogeneous nonlinearities

The(2 1)-dimensional nonlinear Schr(o)dinger(NLS)equation with spatially inhomogeneous nonlinearities is investigated,which describes propagation of light in(2 1)-dimensional nonlinear optical media with inhomogeneous nonlinearities.New types of optical modes and nonlinear effects in optical media are presented numerically.The results reveal that the regular split of beam can be obtained in (2 1)-dimensional nonlinear optical media with inhomogeneous nonlinearities,by adjusting the guiding parameter.Furthermore,the stability of beam regular split is discussed numerically,and the results reveal that the beam regular split is stable to the finite initial perturbations.     

EPR and optical spectra of cupric ions doped in powder strontium maleate tetrahydrate and magnesium Bis (hydrogen maleate) hexahydrate

Abstract

EPR spectra of Cu²⁺ ions doped in a strontium maleate tetrahydrate and magnesium bis (hydrogen maleate) hexahydrate have been studied in X-band at room temperature and at liquid nitrogen temperature. Spin-Hamiltonian parameters have been calculated. Molecular orbital coefficients are obtained by correlating optical absorption data with EPR results.     

Persistence in photoconductivity and optical property of nanostructured copper (II) phthalocyanine thin films

The optical and photoconductive properties of nanostructured copper (II) phthalocyanine (CuPc) surface cells have been studied at room temperature (30 °C). The change in the conductivity of the surface type sample cells under illumination of light was studied as a function of duration and wavelength of photoexcitation. The photoconductivity spectrum of a film of CuPc surface cell does not agree with the absorption spectrum. Particularly for the photoexciting wavelengths in the region 400–500 nm, the photoconductivity shows an appreciable value (or comparatively higher value), although the absorbance in this region is minimum or very less. The change in current under illumination of light and after turning it off has indicated that photoinduced effects persist for a longer period of time even after turning off the illumination of light of various wavelengths and duration. An increase in persistence in photocurrent was noticed with the repeated exposure within a short interval of time. Such studies are important for searching new types of electrically conducting systems (semiconductors) in the form of nanostructured thin films for use as photoactive materials in optoelectronic and memory devices.     

DFT study of magnetic coupling in bis(pyridine-2-carboxylate)-copper(II) polymorphs

The method for exchange coupling parameter J calculations using a broken-symmetry treatment is extended to three-dimensional periodic DFT calculations for three antiferromagnetic polymorphic forms of Cu(pca)₂, pca = pyridine-2-carboxylate. The calculated values (<1 cm⁻¹) are slightly underestimated in comparison with experimental data. For comparison with the cluster treatment, the J values are rationalized using the nearest-neighbors model for polymeric chains.     

Third-order optical nonlinearities of lead-free (Na1−xKx)0.5Bi0.5TiO3 thin films

(Na_1−xK_x)_0.5Bi_0.5TiO₃ (NKBT) (x = 0.1, 0.2, and 0.3) thin films with good surface morphology and rhombohedral perovskite structure were fabricated on quartz substrates by a sol-gel process. The fundamental optical constants (the band gaps, linear refractive indices and absorption coefficients) of the films were obtained through optical transmittance measurements. The nonlinear optical properties were investigated by Z-scan technique performed at 532 nm with a picosecond laser. A two-photon absorption effect closely related with potassium-doping content was found in thin films, and the nonlinear refractive index n₂ increases evidently with potassium-doping. The real part of the third-order nonlinear susceptibility χ⁽³⁾ is much larger than its imaginary part, indicating that the third-order optical nonlinear response of the NKBT films is dominated by the optical nonlinear refractive behavior. These results show that NKBT thin films have potential applications in nonlinear optics.     

Synthesis, crystal structure, Cu doped EPR and voltammetric studies of bis[N-(2-hydroxyethyl)ethylenediamine]zinc(II) squarate monohydrate

Crystal structure of [Zn(hydet-en)₂]·C₄O₄·H₂O (ZHES) (hydet-en is N-(2-hydroxyethyl)ethylenediamine) complex has been synthesized and characterized by analytical, spectroscopic (IR, UV/Vis) and voltammetric techniques. After doping Cu²⁺ ion, its magnetic environment has been identified by electron paramagnetic resonance (EPR) technique. The title complex crystalizes in monoclinic system with space group P2₁/c and with Z=4. Each hydet-en ligand acts as a tridentate ligand through the two N atoms and the hydroxyl O atom, resulting in a six coordinate Zn(II) ion. The EPR spectra were recorded in three perpendicular planes of Cu²⁺ doped ZHES single crystal. The calculated g and A values indicated that the paramagnetic center is rhombic symmetry with the Cu²⁺ ion having distorted octahedral environment. The molecular orbital bond coefficients of the Cu(II) ion in d⁹ state is also calculated by using EPR and optical absorption parameters. The dianion SQ²⁻ is oxidized reversibly in two consecutive steps to the corresponding radical monoanion and neutral form.     

Solvatochromism of Ternary Iron (II) Diimine Cyanide Complexes in 2-Ethyl-2-(hydroxymethyl) 1,3-Propanediol (Trimethylol Propane)

The solvatochromic behaviour of bis-(2,2′-bipyridyl)-biscyanoiron (II) and 2,2′- bipyridyltetracyanoiron (II) in 2-ethyl-2-(hydroxymethyl)-1,3-propanediol has been established. The significance and sensitivities of the solvatochromic shifts of these charge-transfer bands are outlined for the two iron complexes above.     

Raman study of photo‐induced degradation of the Ru(II) complex adsorbed on nanocrystalline TiO2 films

Photo‐induced degradation of a monolayer of the Ru(II) complex adsorbed on anatase TiO₂ thin films was studied by using resonant micro‐Raman spectroscopy. We developed two contrastive experiments to analyze the degradation mechanism. An exponential decay law was found when the dye was irradiated in the absence of a reducing agent. While the sensitized TiO₂ thin film electrode was covered by the I^–/I₃^– redox couple, the dye degradation exhibited a slowed linear decay. The experimental result was compared and the degradation mechanism was analyzed. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Nonlinear optical switching and all-figures of merit in Bi_2S_(3-x)Se_x/PMMA nanocomposite films investigated by Z scan under visible CW laser

Bi2S3-xSex/poly(methyl methacrylate)(PMMA)nanocomposite films were prepared using microwave assisted synthesis with different compositions of x.Crystal structure,surface morphology,and optical properties were investigated to characterize the prepared nanocomposite films.The crystallinity and optical band gap of the prepared Bi2S3-xSex/PMMA were affected by x.The prepared samples showed a blue shift in the absorption edge.The laser power dependent nonlinear refraction and absorption of Bi2S3-xSex/PMMA nanocomposite films were investigated by using the Z-scan technique.The optical nonlinearity of the nanocomposite films exhibited switchover from negative nonlinear refraction to positive nonlinear refraction to negative nonlinear refraction effects,and from saturable absorption to reverse saturable absorption to saturable absorption with an increase and decrease in the composition.An interesting all-optical figure of merit was reported to assess the nanocomposite films for a practical device.It was calculated that the device all-figures of merit were based on the nonlinear response,which is important for the all-optical switching device.The results demonstrate that the optimized all-optical figures of merit can be achieved by adjusting the composition and input laser power,which can be used for the design of different all-photonic devices,and the results of nonlinear switching behavior can open new possibilities for using the nanocomposite films in laser Q-switching and mode-locking.     

Electron paramagnetic resonance and optical absorption studies of manganese ions doped in polyvinyl(alcohol) complexed with polyethylene glycol polymer films

Electron paramagnetic resonance (EPR), optical absorption, and infrared spectral studies have been carried out on Mn²⁺ ions doped in poly(vinyl alcohol) (PVA) complexed with polyethylene glycol (PEG) films prepared by solution cast technique. The EPR spectra of 0.25?mol% Mn²⁺ ions doped polymer complex (PVA+PEG) at room temperature exhibit sextet hyperfine structure (hfs), centered at g????1.99. The spin?CHamiltonian parameter values indicate that the ground state of Mn²⁺ ion is d⁵ and the site symmetry around Mn²⁺ ions in tetragonally distorted octahedral site. The spin concentration participating in the resonance is measured as a function of temperature and it is observed that it obeys Boltzmann??s law. The paramagnetic susceptibility (??) is calculated from the EPR data at various temperatures (93?C333?K) and it obeys the Curie?CWeiss law. The optical absorption spectra exhibits two bands which are assigned to ⁶A_1g (S)??⁴A_1g (G) or ⁴E_g (G) and ⁶A_1g (S)??⁴T_2g (G) transitions. The infrared spectrum exhibits few bands due to the presence of O?CH, C?CH, and C=C groups.     

Origin of third-order optical nonlinearity in Au:SiO(2) composite films on femtosecond and picosecond time scales

Three sorts of probe laser, which have pulse durations of 200 fs, 35 ps, and 70 ps, were employed in the measurement of the third-order nonlinear optical susceptibility x((3)) in Au:SiO(2) composite films in a degenerate four-wave mixing scheme. We found that the composite films at their absorption peak (~550 nm) had a maximum x((3)) , which depends strongly on the pulse width of the probe laser. The value of x((3)) measured with a 70-ps laser was ~30 times larger than that measured with a 200-fs laser. The time-resolved measurements revealed that the optical nonlinearity on the femtosecond time scale is attributable mainly to contributions from the interband electric-dipole transition (especially at low concentrations) and partly to those from hot electrons rather than being dominated by hot-electron excitation in the picosecond regime.     

Presence of Jahn-Teller distortions in a novel six-coordinate Ag(II) complex: temperature dependent EPR,optical and magnetic susceptibility measurements

Single-crystal variable temperature EPR, optical and polycrystalline magnetic susceptibility studies have been made on a novel six-coordinate Ag(II) complex. Temperature dependent EPR studies on pure single crystals of this compound reveal that dynamic Jahn-Teller distortion operates above 230 K, between 230 K and 120K static Jahn-Teller distortion sets in and below 110 K there is evidence of exchange interaction. Crystal g values were obtained by least-squares fitting with the data obtained from the orientation dependent EPR spectra of the undiluted single crystal of this complex at 300 K and 77 K. From an optical study the Jahn-Teller stabilization energy is found to be ～2250cm^?1. Comparison of Abs_max values for other silver(II) compounds enables us to conclude that the formal geometry of this complex is a tetragonally distorted octahedral. Infrared spectra of this complex were also recorded over a wide range of temperature. Magnetic susceptibility measurements over a wide range of temperature on the powder sample of this compound reveal that the complex is antiferromagnetically coupled in the temperature range 5–40 K with 2J = 0.906cm^?1, and above 40K it is ferromagnetically coupled with 2J = +7.4cm^?1. The effective magnetic moment (μ_eff) of this complex has been compared with that of a series of other silver(II) complexes available in the literature. Finally, the spectral and magnetic data of this complex have been compared with those of a corresponding isostructural and isomorphous copper(II) complex.