Synthesis and Properties of a New Photostable Soluble Perylene Dye: N,N'-Di-(1-Dehydroabietyl) Perylene-3,4,9,10-Bis(Dicarboximide)

N,N'-Di-(-1-Dehydroabietyl) perylene-3,4,9,10-bis(dicarboximide) is prepared in 95% yield by the condensation of perylene 3,4,9,10-tetracarboxylic dianhydride with dehydroabietyl amine. Thermal and photostable bright red-orange dye is measured to have a fluorescence quantum yield of unity, Q_f=1, in chloroform solutions. Solubility of the dye is 1.8 g/L in chloroform. The diimide is an ideal reference probe for fluorescence quantum yield measurements in 500—650 nm region and also very interesting dye for chemiluminescent light devices.     

Aggregation-Induced Emission and Temperature-Dependent Luminescence of Potassium Perylenetetracarboxylate

Investigation of temperature-dependent photoluminescent properties of potassium perylene-3,4,9,10-tetracarboxylate (K₄PTC), a molecule with no internal rotational degrees of freedom, shows aggregation-induced enhanced emission at room temperature. The different excitonic emission processes are dependent of temperature, some of which quenches in an intermediate temperature range (from 50 to 150 K). The exciton excited states switching phenomenon from "dark" to "bright" states is observed and its explained using Herzberg-Teller selection rule. K₄PTC is a molecule comparable to the size of its precursor, perylene-3,4,9,10-tetracarboxylic anhydride (PTCDA) and is highly soluble in water, contrary to PTCDA, which is poorly soluble in most solvents. Powder x-ray diffraction measurements corroborate a lesser degree of ordering of bulk K₄PTC compared to bulk PTCDA. The green luminescent molecule could, in principle, be used as a biomarker, or in photodynamic therapy, if further studies show relatively low toxicity.

     

IR absorption anisotropy in perylene-3,4,9,10-tetracarboxylic acid dianhydride

Vacuum-deposited perylene-3,4,9,10-tetracarboxylic acid dianhydride thin films are investigated by IR-spectropolarimetry with variable incident angle of plane-polarized radiation. Anisotropy of absorption bands in the region 700–900 cm⁻¹ is detected. Absorption bands in the subregions 728–736 and 806–810 cm⁻¹ are shown to be of triplet nature with orthogonally oriented dipole moments within the triplet.     

Inhibition of copper corrosion by self-assembled films of new Schiff bases and their modification with alkanethiols in aqueous medium

The inhibitive action of self-assembled films derived from two ligands Schiff bases, including N,N′-ethylen-bis (salicylidenimine) and N,N′-ortho-phenylen-bis (salicylidenimine) on copper surface has been studied by electrochemical techniques in chloride and acidic solutions. It was found that when the concentration of the inhibitors was increased the inhibition efficiency was increased, too. The results of the electrochemical studies have illustrated that the inhibition efficiency of S-o-ph-S is higher than S-E-S. Both the Schiff bases obeyed the Langmuir isotherm and thermodynamics calculations revealed that S-o-ph-S had larger adsorption constant and more negative free energy of adsorption with respect to S-E-S. When the films were modified by propanethiol and 1-dodecanethiol, the corrosion resistance of mixed films was significantly increased.     

Synthesis, characterization and studies on the nonlinear optical parameters of hydrazones

Three hydrazones, 2-(4-methylphenoxy)-N′-[(1E)-(4-nitrophenyl)methylene]acetohydrazide (compound-1), 2-(4-methylphenoxy)-N′-[(1E)-(4-methylphenyl)methylene]acetohydrazide ((compound-2) and N′-{(1E)-[4-(dimethylamino)phenyl]methylene}-2-(4-ethylphenoxy) acetohydrazide(compound-3) were synthesized and their third order nonlinear optical properties were investigated using a single beam z-scan technique with nanosecond laser pulses at 532 nm. Open aperture data obtained from the three compounds indicates two photon absorption at this wavelength. The nonlinear refractive index n₂, the nonlinear absorption coefficient β, the magnitude of the effective third order susceptibility χ⁽³⁾, the second order hyperpolarizability γ_h and the coupling factor ρ have been estimated. The values obtained are comparable with the values obtained for 4-methoxy chalcone derivatives and dibenzylidene acetone derivatives. Among the compounds studied, compounds-1 and 3 exhibited the better optical power limiting behaviour at 532 nm. Our studies suggest that compounds-1, 2 and 3 are potential candidates for optical device applications such as optical limiters and optical switches.     

Air-stable ambipolar organic field effect transistors with heterojunction of pentacene and N,N'-bis(4-trifluoromethylben-zyl)perylene-3,4,9,10-tetracarboxylic diimide

Fabrication of ambipolar organic field-effect transistors (OFETs) is essential for the achievement of an organic complementary logic circuit. Ambipolar transports in OFETs with heterojunction structures are realized. We select pentacene as a P-type material and N,N'-bis(4-trifluoromethylben-zyl)perylene-3,4,9,10-tetracarboxylic diimide (PTCDI-TFB) as a n-type material in the active layer of the OFETs. The field-effect transistor shows highly air-stable ambipolar characteristics with a field-effect hole mobility of 0.18~cm²/(V.s) and field-effect electron mobility of 0.031~cm²/(V.s). Furthermore the mobility only slightly decreases after being exposed to air and remains stable even for exposure to air for more than 60 days. The high electron affinity of PTCDI-TFB and the octadecyltrichlorosilane (OTS) self-assembly monolayer between the SiO₂ gate dielectric and the organic active layer result in the observed air-stable characteristics of OFETs with high mobility. The results demonstrate that using the OTS as a modified gate insulator layer and using high electron affinity semiconductor materials are two effective methods to fabricate OFETs with air-stable characteristics and high mobility.     

Post deposition purification of PTCDA thin films

The decomposition of perylene-3,4,9,10-tetracarboxylic dianhydride (PTCDA) molecules during evaporation of unpurified raw material in ultra high vacuum was studied. The fragments were identified by mass spectrometry and the influence of these fragments and further contaminations of the raw material on the electronic structure of PTCDA thin films was measured by photoemission spectroscopy. Annealing of contaminated PTCDA films was tested as cheap and easy to perform method for (partial) post deposition purification of the contaminated films.     

Experimental and theoretical study for corrosion inhibition of mild steel in hydrochloric acid solution by some new hydrazine carbodithioic acid derivatives

The corrosion inhibition of mild steel in 0.5 M hydrochloric acid solutions by some new hydrazine carbodithioic acid derivatives namely N′-furan-2-yl-methylene-hydrazine carbodithioic acid (A), N′-(4-dimethylamino-benzylidene)-hydrazine carbodithioic acid (B) and N′-(3-nitro-benzylidene)-hydrazine carbodithioic (C) was studied using chemical (weight loss) and electrochemical (potentiodynamic and electrochemical impedance spectroscopy, EIS) measurements. These measurements show that the inhibition efficiency obtained by these compounds increased by increasing their concentration. The inhibition efficiency follow the order C > B > A. Polarization studies show that these compounds act as mixed type inhibitors in 0.5 M HCl solutions. These inhibitors function through adsorption following Langmuir isotherm. The electronic properties of these inhibitors, obtained using PM3 semi-empirical self-consistence field method, have been correlated with their experimental efficiencies using non-linear regression method.     

Self-aggregates formation of 3,4,9,10-tetra-(n-alkoxy-carbonyl)-perylenes in Langmuir-Blodgett films

Langmuir-Blodgett (LB) films formed of some 3,4,9,10-tetra-(n-alkoxy-carbonyl)-perylenes and of their binary mixtures with the liquid crystal 4-octyl-4′-cyanobiphenyl (8CB) have been studied. Absorption and fluorescence studies were carried out. Both absorption and fluorescence spectra have revealed the formation of self-aggregates of dye molecules in monomolecular layers. Moreover, information about the molecular organization at the air-solid substrate interface has been obtained.     

Photoluminescence properties of vacuum-deposited organic molecule-oxide (MePTCDI-SiO2) mixed layers

Thin films of the perylene derivative N,N′-dimethylperylene-3,4,9,10-bis-dicarboximide (MePTCDI) incorporated in SiO₂ matrix at various concentrations are obtained by condensation of host and dye in high vacuum. Photoluminescence spectroscopy is applied to study the spectral properties of the layers. Significant alterations in luminescence spectra in dependence on dye quantity are explained as a consequence of dye aggregation and resonant energy transfer. We demonstrate that the deposition geometry and preparation conditions offer an effective way to reduce the possibilities for non-radiative transitions, thus increasing the photoluminescence quantum efficiency.     

Simultaneous estimation of optical nonlinear refractive and absorptive parameters by solvent induced changes in optical density

With picosecond pulses at the wavelength of 532 nm, we have determined the optical nonlinear refractive and absorptive parameters of the dye N,N′-bis(2,5-di-tert-butylphenyl)-3,4,9,10-perylenedicarboximide (DBPI) by a single closed-aperture (CA) Z-scan technique. This technique uses a theoretical model that elucidates the refractive and absorptive optical nonlinearity present simultaneously in the CA Z-scan profile. The observed remarkable red shift in the absorption spectrum of the dye in the acidic medium as compared to that in the polar medium has been used to vary the optical density at a single frequency. We find that the effect of saturable absorption (SA) is complete at higher concentrations. The effect of reverse saturable absorption (RSA) is dominating in dilute concentrations. The observed variations in the excited state refractive cross-section (σ_r) with the concentration and the energy have been attributed to the contributions of higher order nonlinearity along with the existing third-order nonlinearity.     

Structure of Epitaxial Layers of KCl on Ag(100)

We investigated the epitaxial growth of thin KCl films on Ag(100) by spot-profile-analysis low energy electron diffraction (SPA-LEED) and scanning tunnelling microscopy (STM). The structural relation of the (100)-oriented KCl film with respect to the Ag(100) surface is incommensurate, nevertheless the structural quality is very high and terraces with an average diameter of 250 Å are obtained. The unit cells of KCl and Ag(100) are aligned, and there is no rotational mosaicity as present in the case of NaCl on Ag(100). We attribute this to a small interaction between KCl and Ag(100) and growth starting at step edges of the metal substrate. In order to demonstrate the high structural quality of the KCl films, we deposited a monolayer of perylene-3,4,9,10-tetracarboxylic acid dianhydride (PTCDA) on these films. We obtained the identical monolayer structure that was observed earlier on bulk KCl. We thus suggest that KCl/Ag(100) is ideal for surface experiments on thin dielectric films.     

Influence of dipole moments on light-emitting features of cardo-type 1H-pyrazolo[3,4-b]quinolines

Several 1H-pyrazolo[3,4-b]quinoline derivatives were synthesized from 9,9′-di(p-aminophenyl)fluorene as possible dye chromophore for the organic light-emitting diodes. All the compounds exhibit strong fluorescence in solution and in solid state as well. The maximally achieved brightness was 65 Cd/m² and spectral range of electroluminescence (EL) covers the wavelength ranges from 420 up to 470 nm. The prepared compounds were used as dye luminophores in poly(N-vinylcarbazole) (PVK) matrix for single-layer EL light-emitting device. Principal goal of the work consists in an establishment of a possibility to operate by their light-emitting features (spectral positions of emitting lines, efficiency of electroluminescence, brightness, etc.) by appropriate changes of state dipole moments of the particular chromophore determined by semi-empirical quantum chemical calculations. The principal physical mechanism of such effects is explained within dipole-dipole interactions between the dye chromophores and PVK polymer chains.     

Structural analysis of PTCDA monolayers on epitaxial graphene with ultra-high vacuum scanning tunneling microscopy and high-resolution X-ray reflectivity

Epitaxial graphene, grown by thermal decomposition of the SiC (0001) surface, is a promising material for future applications due to its unique and superlative electronic properties. However, the innate chemical passivity of graphene presents challenges for integration with other materials for device applications. Here, we present structural characterization of epitaxial graphene functionalized by the organic semiconductor perylene-3,4,9,10-tetracarboxylic dianhydride (PTCDA). A combination of ultra-high vacuum scanning tunneling microscopy (STM) and high-resolution X-ray reflectivity (XRR) is used to extract lateral and vertical structures of 0, 1, and 2 monolayer (ML) PTCDA on epitaxial graphene. Both Fienup-based phase-retrieval algorithms and model-based least-squares analyses of the XRR data are used to extract an electron density profile that is interpreted in terms of a stacking sequence of molecular layers with specific interlayer spacings. Features in the STM and XRR analysis indicate long-range molecular ordering and weak π–π* interactions binding PTCDA molecules to the graphene surface. The high degree of both lateral and vertical ordering of the self-assembled film demonstrates PTCDA functionalization as a viable route for templating graphene for the growth and deposition of additional materials required for next-generation electronics and sensors.     

Photophysical characteristics of three novel benzanthrone derivatives: Experimental and theoretical estimation of dipole moments

The effect of solvents on absorption and fluorescence spectra and dipole moments of novel benzanthrone derivatives such as 3-N-(N′,N′-Dimethylformamidino) benzanthrone (1), 3-N-(N′,N′-Diethylacetamidino) benzanthrone (2) and 3-morpholinobenzanthrone (3) have been studied in various solvents. The fluorescence lifetime of the dyes (1-3) in chloroform were also recorded. Bathochromic shift observed in the absorption and fluorescence spectra of these molecules with increasing solvent polarity indicates that the transitions involved are π→π^?. Using the theory of solvatochromism, the difference in the excited-state (μ_e) and the ground-state (μ_e) dipole moments was estimated from Lippert-Mataga, Bakhshiev, Kawski-Chamma-Viallet, and McRae equations by using the variation of Stokes shift with the solvent’s relative permittivity and refractive index. AM1 and PM6 semiempirical molecular calculations using MOPAC and ab-initio calculations at B3LYP/6-31 G^? level of theory using Gaussian 03 software were carried out to estimate the ground-state dipole moments and some other physicochemical properties. Further, the change in dipole moment value (Δμ) was also calculated by using the variation of Stokes shift with the molecular-microscopic empirical solvent polarity parameter (E_T^N). The excited-state dipole moments observed are larger than their ground-state counterparts, indicating a substantial redistribution of the π-electron densities in a more polar excited state for all the systems investigated.     

Physical properties of NxTiO2 prepared by sol–gel route

The compounds N_xTiO₂(x=0, 0.05, 0.1, 0.2) with the anatase structure have been synthesized by Sol–Gel method using Tri-ethyl Amine as nitrogen source and their optical, electrical and electrochemical properties are investigated. The electrical conductivity and thermoelectric power are measured in the temperature rang 300–600 K. The samples exhibit p-type behavior in contrast to TiO₂. The doped-samples exhibit two optical transitions (2.35≤E_h−Vis(eV)≤2.55; 1.97≤E_l−Vis (eV)≤2.06) directly allowed in the visible region, while only one transition is observed in UV region (E_UV∼3.00 eV). Pure TiO₂ shows direct band gap transition of 3.17 eV. The results confirm experimentally the calculations of Di. Valentin et al. [42]. The transitions E_h−Vis and E_l−Vis are attributed respectively to the promotion of electrons from the localized N 2p and π^? N–O bond to the conduction band. In all cases, E_UV is associated to the forbidden band energy. Though that the conductivity is generally improved by doping process, only N_0.05TiO₂ and N_0.1TiO₂ shows an enhanced mobility. The mechanism of conduction takes place by small polaron hopping. The band edge positions of N_xTiO₂ (x=0, 0.05, 0.1, 0.2) at room temperature is predicted from the obtained physical properties. This study proves experimentally the principal role of nitrogen in doping process and permits the electronic states localization associated with N-impurities in TiO₂ anatase.     

Crystal growth,structural and optical properties of an organic ion-complex crystal: 4-N,N-dimethylamino-4′-N′-methylstilbazolium iodide

4-N,N-dimethylamino-4′-N′-methylstilbazolium iodide (DMSI) compound was synthesized by Knoevenagel reaction method and the crystals were grown by solution growth method. From the single crystal X-ray diffraction study, it is confirmed that DMSI crystal belongs to monoclinic system. The bond-length alternation (BLA) of the DMSI molecule was found to be 0.11 Å, which is responsible for quadratic NLO response. The electronic transition properties and optical constants such as energy gap (E_g), linear refractive index (n₁) were determined using UV–visible and photoluminescence spectral studies. The second order nonlinear optical property of the crystal was examined using Kurtz–Perry powder test. Laser induced damage threshold on (0 0 1) plane of the optically polished crystal was found to be 1.24 GW/cm².     

Synthesis of a New Thermal and Photostable Reference Probe for Qf Measurement in Aqua: Water Soluble N,N′-bis-(2-Hydroxy-4-benzoic Acid)-3,4,9,10-perylenebis(dicarboximide)

N,N′-bis(2-hydroxy-4-benzoic acid)-3,4,9,10-perylenebis(dicarboximide) is synthesized from perylene 3,4,9,10-tetracarboxylic dianhydride and 4-amino-3-hydroxy benzoic acid in 90% yield. Together with the photostability the dye is also very stable thermally. The fluorescence quantum yield is measured as one, Q_f=1.The diimide dissolves in water at PH = 8 completely. The diimide is an ideal reference probe for fluorescence quantum yield measurements in 500–650 nm region and an attractive photosensitizer for the photoreactions occur in water.     

Transparent nano composite PVA–TiO2 and PMMA–TiO2 thin films: Optical and dielectric properties

Transparent nano composite PVA–TiO₂ and PMMA–TiO₂ thin films were prepared by an easy and cost effective dip coating method. Al/PVA–TiO₂/Al and Al/PMMA–TiO₂/Al sandwich structures were prepared to study the dielectric behavior. The presence of metal–oxide (Ti–O) bond in the prepared films was confirmed by Fourier transform infrared spectroscopy. X-ray diffraction pattern indicated that the prepared films were predominantly amorphous in nature. Scanning electron micrographs showed cluster of TiO₂ nanoparticles distributed over the film surface and also there were no cracks and pin holes on the surface. The transmittance of the films was above 80% in the visible region and the optical band gap was estimated to be about 3.77 eV and 3.78 eV respectively for PVA–TiO₂ and PMMA–TiO₂ films by using Tauc's plot. The determined refractive index (n) values were between 1.6 and 2.3. High value of dielectric constant (?′ = 24.6 and ?′ = 26.8) was obtained for the prepared composite films. The conduction in the composite films was found to be due to electrons. The observed amorphous structure, good optical properties and dielectric behavior of the prepared nano composite thin films indicated that these films could be used in opto-electronic devices and in thin film transistors.