Photo- and electroluminescent properties of zinc(II) complexes with tetradentate Schiff bases,derivatives of salicylic aldehyde

It is studied how the introduction of various substituents into the composition of organic ligands affects the photoluminescence spectra of new zinc(II) complexes with tetradentate Schiff bases H₂L (derivatives of salicylic aldehyde (H₂SAL1, H₂SAL2) and o-vanillin (H₂MO1, H₂MO2) with ethylenediamine and o-phenylenediamine) in the form of bulk solids and thin films. It is demonstrated that the emission spectra of bulk solid complexes without o-phenylenediamine bridges (ZnSAL1 and ZnMO1) contain additional long-wavelength bands compared to the spectra of corresponding thin films. In the case of films obtained from [ZnSAL1]₂ dimer complexes, the long-wavelength band is dominant. At the same time, the photoluminescence spectra of ZnSAL2 and ZnMO2 complexes with o-phenylenediamine bridges are similar in the case of solid samples and thin films. The electroluminescent properties of organic light-emitting diodes (OLEDs) with the ITO/α-NPD/ZnL/Ca:Al structure are studied. The bathochromic shift of the electroluminescence peaks of OLEDs with respect to the photoluminescence spectra of bulk solid samples and thin films is probably related to the formation of exciplexes at the α-NPD/ZnL interface. The electroluminescence spectra of OLEDs based on [ZnSAL1]₂ show a hypsochromic shift of the emission maximum, which can be caused by a shift of the recombination region into the α-NPD layer.     

Vibrational Behavior of Transition Metal Cupferronato Complexes: Raman Studies on Cobalt(II) Cupferronato Derivatives

The FT-Raman spectrum of cupferron, [PhN₂O₂]NH₄ and the micro-Raman spectra of the new corresponding cobalt(II) cupferronato complexes, CoL₂A₂, L = PhN₂O₂, a = H₂O, MeOH, o-C₆H₄(NH₂)₂, p-C₆H₄(NH₂)₂ and CoL₂A, a = (-C₆H₄NH₂-p)₂ were recorded and discussed. All the complexes show a Raman band at about 1302 cm¹ and the characteristic v(N-N) and δ(ONNO) modes of the anionic ligand. the vibrational analysis of the title compounds reveals the electron delocalisation over the N-nitroso-N-hydroxylaminato (ONNO) unit, as well as the bidentate coordination of the cupferronato ligand to the metal center through the oxygen atoms.     

The properties of free polymer surfaces and their influence on the glass transition temperature of thin polystyrene films

We present a detailed study of free polymer surfaces and their effects on the measured glass transition temperature (T_g) of thin polystyrene (PS) films. Direct measurements of the near-surface properties of PS films are made by monitoring the embedding of 10 and 20 nm diameter gold spheres into the surface of spin-cast PS films. At a temperature T = 378K( > T_g), the embedding of the spheres is driven by geometrical considerations arising from the wetting of the gold spheres by the PS. At temperatures below T_g ( 363K < T < 370K), both sets of spheres embed 3-4 nm into the PS films and stop. These studies suggest that a liquid-like surface layer exists in glassy PS films and also provide an estimate for the lower bound of the thickness of this layer of 3-4 nm. This qualitative idea is supported by a series of calculations based upon a previously developed theoretical model for the indentation of nanoscale spheres into linear viscoelastic materials. Comparing data with simulations shows that this surface layer has properties similar to those of a bulk sample of PS having a temperature of 374 K. Ellipsometric measurements of the T_g are also performed on thin spin-cast PS films with thicknesses in the range 8nm < h < 290nm. Measurements are performed on thin PS films that have been capped by thermally evaporating 5 nm thick metal (Au and Al) capping layers on top of the polymer. The measured T_g values (as well as polymer metal interface structure) in such samples depend on the metal used as the capping layer, and cast doubt on the general validity of using evaporative deposition to cover the free surface. We also prepared films that were capped by a new non-evaporative procedure. These films were shown to have a T_g that is the same as that of bulk PS (370±1 K) for all film thicknesses measured (> 7 nm). The subsequent removal of the metal layer from these films was shown to restore a thickness-dependent T_g in these samples that was essentially the same as that observed for uncapped PS films. An estimate of the thickness of the liquid-like surface layer was also extracted from the ellipsometry measurements and was found to be 5±1 nm. The combined ellipsometry and embedding studies provide strong evidence for the existence of a liquid-like surface layer in thin glassy PS films. They show that the presence of the free surface is an important parameter in determining the existence of T_g reductions in thin PS films.     

X-ray photoelectron investigation of charge distribution in copper(II) phthalocyanine complexes

The charged states of atoms in unsubstituted copper(II) phthalocyanine (CuPcH₁₆) and hexade-cafluorinated copper(II) phthalocyanine (CuPcF₁₆) complexes and in thin films of them deposited on silicon substrates by vacuum thermal evaporation are investigated by X-ray photoelectron spectroscopy (XPS). The C(1s), N(1s), Cu(2p) core level energies and the charged states of atoms in the studied complexes are calculated using the DFT method. The performed experimental study and theoretical calculations show that the introduction of electron acceptor substituents into benzene rings mostly affects the atoms of benzene rings and insignificantly affects the charge state of nitrogen atoms in the pyrrole ring.     

Development and integration of near atmospheric N2 ambient sputtered Au thin film for enhanced infrared absorption

The exceedingly fragile nature of thermally grown Au-black coating makes handling and patterning a critical issue. Infrared absorption characteristics of near atmospheric, N₂ ambient DC sputtered Au thin films are studied for this purpose. The thin Au films are sputtered at different chamber pressures in Ar and N₂/Ar gas ambient from 4.5 to 8.0 mbar and optimized for enhanced infrared absorption. The absorber film sputtered in N₂/Ar ambient at 8.0 mbar chamber pressure offers significant absorption of medium to long wave infrared radiations. The micro-patterning of sputtered Au thin film is carried out by using conventional photolithography and metal lift off methods on a prefabricated µ-infrared detector array on Si (1 0 0) substrate. The steady state temperature response of sputtered film has been examined using nondestructive thermal imaging method under external heating of the detector array.     

Photoacoustic spectroscopy of thin films of As<Subscript>2</Subscript>S<Subscript>3</Subscript>, As<Subscript>2</Subscript>Se<Subscript>3</Subscript> and GeSe<Subscript>2</Subscript>

Photoacoustic spectroscopy (PAS) is one of the important branches of spectroscopy, which enables one to detect light-induced heat production following the absorption of pulsed radiation by the sample. As₂S₃, As₂Se₃ and GeSe₂ exhibit a wide variety of photo-induced phenomena that enable them to be used as optical imaging or storage medium and various electronic devices, including electro-optic information storage devices and optical mass memories. Therefore, accurate measurement of thermal properties of semiconducting films is necessary to study the memory density. The thermal conductivity of thin films of As₂S₃ (thickness 100 μm and 80 μm), As₂Se₃ (thickness 100 μm and 80 μm) and GeSe₂ (thickness 120 μm and 100 μm) has been measured using PAS technique. Our result shows that the thermal conductivity of thicker films is larger than the thinner films. This can be explained by the thermal resistance effect between the film and the surface of the substrate.      

Synthesis, DNA-binding, Cytotoxicity, Photo Cleavage, Antimicrobial and Docking Studies of Ru(II) Polypyridyl Complexes

Three Ruthenium(II) polypyridine complexes, [Ru(phen)₂(mipc)]²⁺(1), [Ru(bpy)₂(mipc)]²⁺ (2) and [Ru(dmb)₂(mipc)]²⁺(3) [mipc?=?2-(6-methyl-3-(1H-imidazo[4, 5-f][1,10]-phenanthroline-2-yl)-4H-chromene-4-one, phen?=?1,10-phenanthroline,bpy?=?2, 2′bipyridine,dmb?=?4, 4′-dimethyl-2, 2′-bipyridine] have been synthesized and characterized by elemental analysis, IR, UV–Vis, ¹H& ¹³C NMR and mass spectra. The DNA-binding properties of the Ruthenium(II) complexes were investigated by spectrophotometric methods, viscosity measurements and light switch studies. These three complexes have been focused on photo activated cleavage studies with pBR-322 and antimicrobial studies. Experimental results indicate that the three complexes intercalate into DNA base pairs and follows the order of 1?>?2?>?3 respectively. Molecular docking studies also support the DNA interactions with complexes through hydrogen bonding and vander Waal’s interactions. Cytotoxicity studies with Hela cell lines has been revealing about anti tumor activity of these complexes.     

THE SYNTHESIS AND SPECTRAL CHARACTERIZATION OF NEW Cu(II), Ni(II), Co(III), AND Zn(II) COMPLEXES WITH SCHIFF BASE

ABSTRACT

Cu(II), Ni(II), Co(III) and Zn(II) complexes with Schiff base have been prepared. Ligand is derived from condensation of 1,2-bis(p>-aminophenoxy)ethane and 2- hydroxynaphthalin-1-carbaldehyde. The complexes have been characterized by elemental analyses, Λ_M, IR, UV-VIS, ¹H NMR, ¹³C NMR and magnetic measurements. The ligand is coordinated to the central metal as a tetradentade ONNO ligand. The four bonding sites are the azomethine nitrogen and aldehydic -OH groups.     

Luminescent Langmuir-Blodgett film of a new amphiphilic Eu β-diketonate

This work reports on the synthesis and characterization of the ligand 3-hexadecylpentane-2,4-dione (Hhdacac) and its Eu³⁺ complexes Eu(hdacac)₆·2H₂O, Eu(hdacac)₆·phen and Eu(hdacac)₆·tta, where phen and tta denote 1,10-phenanthroline and thenoyltrifluoroacetone, respectively. These new compounds present long carbon chains and their expected miscibility into non-polar ambients is confirmed by the emission spectra of Eu(hdacac)₆·tta in hexane. Moreover, the amphiphilic properties of Eu(hdacac)₆ complexes allow the obtainment of thin luminescent films by the Langmuir-Blodgett technique. In both cases (solids and films), the typical antenna effect of β-diketonates is observed. The alluring characteristics of these compounds raise great interest in many fields of Materials Science, like photo- and electro-luminescent materials (mainly thin “organic” films), metal catalysts or probes in non-polar solutions, and Langmuir-Blodgett films of several compositions. For the characterization of these products, nuclear magnetic resonance spectroscopy (¹H NMR), thermogravimetric analysis, elementary analyses (C, H), scanning electron microscopy (energy dispersive X-ray spectroscopy), absorption (UV-vis/FT-IR) and photoluminescence spectroscopies were used.     

Electrical and optical properties of Jäger-nickel (II)-based molecular-material thin films prepared by the vacuum thermal evaporation technique

Semiconductor molecular-material thin films of [6,13-Ac₂-5,14-Me₂-[14]-4,6,11,13-tetraenato-1,4,8,11-N₄] and the bidentate amines 1,4-diaminebutane, 1,12-diaminedodecane and 2,6-diamineanthraquinone have been prepared by vacuum thermal evaporation on corning glass substrates and crystalline silicon wafers. The films thus obtained were characterized by infrared (FTIR), ultraviolet-visible (UV-VIS) and photoluminescence (PL) spectroscopies. The surface morphology, thickness and structure of these films were analyzed by atomic force microscopy (AFM), ellipsometry and X-ray diffraction (XRD), respectively. IR spectroscopy showed that the molecular-material thin films exhibit the same intra-molecular bonds as the original compounds, which suggests that the thermal evaporation process does not significantly alter their bonds. The effect of temperature on conductivity was also measured in these samples; it was found that the temperature-dependent electric current is always higher for the voluminous amines with large molecular weights and suggests a semiconductor behavior with conductivities in the order of 10⁻⁶-10⁻¹ Ω⁻¹ cm⁻¹. Finally, the optical band gap (E_g) and cubic χ⁽³⁾ non-linear optical (NLO) properties of these amorphous molecular complexes were also evaluated from optical absorption and optical third harmonic generation (THG) measurements, respectively.     

Influence of annealing on the structure formation and optical absorption parameters of 2-(2,3-dihydro-1,5-dimethyl-3-oxo-2-phenyl-1H-pyrazol-4-ylimino)-2-(4-nitrophenyl) acetonitrile thin films

The effect of annealing temperatures (343 and 425) K on structure formation and optical absorption of 2-(2,3-dihydro-1,5-dimethyl-3-oxo-2-phenyl-1H-pyrazol-4-ylimino)-2-(4-nitrophenyl)acetonitrile (DOPNA) thin films has been reported. The structural properties are investigated by X-ray diffraction and transmission electron microscope techniques. The electronic transitions of DOPNA thin films are investigated in terms of ultravioletvisible (UV-vis) spectroscopy. The absorption coefficient of films has been calculated and analyzed in order to determine the type of inter-band electronic transition as well as the value of optical band gap for films. The films have been found to have indirect allowed optical band gap: which was found to decrease by increasing annealing temperatures.     

Influence of Copper(II) Ions on Radicals in DOPA–Melanin

DOPA–melanin (DOPA = 3,4-dihydroxyphenyl-alanine) complexes with Cu(II) cations were studied by electron paramagnetic resonance (EPR) spectroscopy. After the addition of metal cations to the melanin polymer, the EPR spectra parameters were measured. The axial g-factor values are g _|| = 2.20 and g _^ = 2.0 5 g_{ \bot } = 2.0 5 . Since $ g_{||} > g_{ \bot } > 2 $ g_{||} > g_{ \bot } > 2 , the ground state orbital of the unpaired electron of the Cu(II) complex is | x ²  -   y ² ñ \left| {{{x}}^{ 2} } \right. \, - \, \left. {{{y}}^{ 2} } \right\rangle . Square coordination of these cations in melanin is proposed. The influence of the Cu(II) concentration in solution used during synthesis on the concentration of melanin radicals was investigated. Cu(II) cations causes the decrease in the paramagnetic center concentration in melanin. The Cu(II) EPR spectra are not saturated within the microwave power range of 0.7–70 mW used in our experiment.     

Investigation of third-order nonlinear optical properties of NNDC-doped PMMA thin films by Z-scan technique

A novel chalcone derivative, (2E)-1-(2,4-di- chloro-5-fluorophenyl)-3-[4-dimethylamino)phenyl]prop-2-en-1-one, abbreviated as NNDC, was prepared and characterized by elemental analyses, infrared (IR) and proton nuclear magnetic resonance (¹H NMR) spectrum, and thermal analyses. The NNDC-doped poly(methyl methacrylate) (PMMA) thin films with five different doping concentrations by weight were prepared by using a spin-coating method. Their linear optical properties were investigated by using a prism coupling measuring system. The third-order nonlinear optical properties of NNDC in 1,2-dichloroethane (NNDC/1,2-dichloroethane) solution and NNDC-doped PMMA (NNDC/PMMA) films were investigated by using the laser Z-scan technique with 20 ps pulses at 532 nm. A self-focusing effect was observed from the Z-scan curves for solution and thin films and the nonlinear refractive index of the film increases with the increase of the doping concentration. In addition, nonlinear absorption was negligible for all samples. The magnitude of third-order nonlinear refraction index n ₂ and the third-order nonlinear susceptibility χ ⁽³⁾ for thin films were 10⁻¹⁵ m²/W and 10⁻⁹ esu, respectively, which are about three orders larger than that of NNDC/1,2-dichloroethane solution. Some necessary analyses were presented. The results show that this material is a promising candidate for application in the nonlinear optical devices at 532 nm.     

Effects of preannealing temperature of ZnO thin films on the performance of dye-sensitized solar cells

The preferred (002) orientation zinc oxide (ZnO) nanocrystalline thin films have been deposited on FTO-coated glass substrates by sol–gel spin-coating technology and rapid thermal annealing for use in dye-sensitized solar cells (DSSC). The effects of preannealing temperature (100 and 300°C) on the microstructure, morphology and optical properties of ZnO thin films were studied. The ZnO thin films were characterized by X-ray diffraction (XRD), scanning electron microscopic (SEM) and Brunauer–Emmett–Teller (BET) analysis. The photoelectric performance of DSSC was studied by I–V curve and the incident photon-to-current conversion efficiency (IPCE), respectively. From the results, the intensities of (002) peaks of ZnO thin films increases with increasing preannealing temperature from 100°C to 300°C. The increase in pore size and surface area of ZnO films crystallized at the increased preannealing temperature contributed to the improvement on the absorption of N3 dye onto the films, the short-circuit photocurrent (J _sc) and open-circuit voltage (V _oc) of DSSC. The higher efficiency (η) of 2.5% with J _sc and V _oc of 8.2 mA/cm² and 0.64 V, respectively, was obtained by the ZnO film preannealed at 300°C.     

Magnetic circular dichroism studies of the charge-transfer transitions in tetrachloro and tetrabromocomplexes of transition metal ions

We report on a detailed study of the temperature dependence of the magnetic circular dichroism spectra of the tetrabromo and tetrachloro-complexes of Cu(II), Fe(III) and Co(II) through their charge transfer absorption bands. All M.C.D. and absorption spectra were measured as far as about 44 000 cm^-1 on polymer films obtained by evaporating an acetonitrile solution of cellulose diacetate doped with the metal complex. This investigation considerably extends our previous room temperature M.C.D. work and leads to more reliable and detailed spectroscopic assignments than absorption spectra alone. A moment analysis of the FeBr₄ ^- spectra further indicates that non-cubic metal-halogen stretching modes play an important role in the band broadening mechanism. Our data also confirm that the highest occupied orbitals of mainly ligand character occur throughout the series in the order 1e<3t ₂<t ₁.     

Interaction of dimethylsulfoxide and diethylsulfoxide complexes of platinum(II) with bovine serum albumin

We have used electronic absorption spectroscopy in the UV region to study the interaction of a dimethylsulfoxide complex of platinum(II) (cis-[Pt(DMSO)₂Cl₂]) and a diethylsulfoxide complex of platinum (II) (cis-[Pt(DESO)₂Cl₂]) with bovine serum albumin (BSA). We have calculated the physicochemical binding parameters for binding with BSA (the binding constants and the Hill coefficient). We found that sulfoxide ligands promote an increase in the rate of binding of the complexes with BSA. Binding of cis-[Pt(DMSO)₂Cl₂] and cis-[Pt(DESO)₂Cl₂] with BSA leads to a decrease in the thermal stability of the protein. The leaving groups in the complexes for binding with BSA are the sulfoxide molecules, and the mechanism for binding between the dialkylsulfoxide complexes and the protein remains unchanged.     

Synthesis and characterization of electron beam evaporated LiCoO<Subscript>2</Subscript> thin films

LiCoO₂ thin films were prepared by electron beam evaporation technique using LiCoO₂ target with Li/Co ratio 1.1 in an oxygen partial pressure of 5 × 10⁻⁴ mbar. The films prepared at substrate temperature T _s < 573 K were amorphous in nature, and the films prepared at T _s > 573 K exhibited well defined (104), (101), and (003) peaks among which the (104) orientation predominates. The X-ray photoelectron spectroscopy (XPS) and inductively coupled plasma (ICP) data revealed that the films prepared in the substrate temperature range 673–773 K are nearly stoichiometric. The grain size increases with an increase of substrate temperature. The Co–e_g absorption bands, are empty and their peak position lies at around 1.7 eV above the top to the Co–t_2g bands. The fundamental absorption edge was observed at 2.32 eV. The films annealed at 1,023 K in a controlled oxygen environment exhibit (104) out plane texture with large grains. Paper presented at the Third International Conference on Ionic Devices (ICID 2006), Chennai, Tamilnadu, India, Dec. 7–9, 2006     

Synthesis and characterization of Zn(O,OH)S and AgInS2 layers to be used in thin film solar cells

In this paper AgInS₂ and Zn(O,OH)S thin films were synthesized and characterized. AgInS₂ layers were grown by co-evaporation from metal precursors in a two-step process, and, Zn(O,OH)S thin films were deposited from chemical bath containing thiourea, zinc acetate, sodium citrate and ammonia. X-ray diffraction measurements indicated that AgInS₂ thin films grown with chalcopyrite structure, and the as-grown Zn(O,OH)S thin films were polycrystalline. It was also found that the AgInS₂ films presented p-type conductivity, a high absorption coefficient (greater than 10⁴ cm⁻¹) and energy band-gap E_g of about 1.95 eV, Zn(O,OH),S thin films presented E_g of about 3.89 eV. Morphological analysis showed that under this synthesis conditions Zn(O,OH),S thin films coated uniformly the absorber layer. Additionally, the Zn(O,OH)S kinetic growth on AgInS₂ layer was studied also. Finally, the results suggest that these layers possibly could be used in one-junction solar cells and/or as top cell in a tandem solar cell.     

DFT study of the effect of different metals on structures and electronic spectra of some organic-metal compounds as sensitizing dyes

Ruthenium polypyridined-derivative complexes are used in dye-sensitized solar cell [DSSC] as a light to current conversion sensitizer. In order to lower the cost of the DSSC the normal transition metals were used to replace the noble metal ruthenium, and some compounds [ML₂L′] (M = Pt, Fe, Ni, Zn; L = isonicotinic acid, L′ = maleonitriledithiolate, I = PtL₂L′, II = FeL₂L′, III = NiL₂L′, IV = ZnL₂L′) were selected as the replacement. The geometries, electronic structures and optical absorption spectra of these compounds have been studied by using density functional theory (DFT) calculation at the B3LYP/LANL2DZ, B3P86/LANL2DZ, B3LYP/GEN level of theory. All the geometric parameters are close to the experimental values. The HOMOs are mainly on the maleonitriledithiolate groups mixed with fewer characters of the metal atom, the LUMOs are mainly on the two pyridine ligands. This means that the electron transition is attributed to the LLCT. The maximum absorptions of complexes are found to be at 351 nm, 806 nm for compound I, and 542 nm for compound II. The maximum absorptions of complexes are found to be at 884 nm for compound III, and 560 nm for compound IV. This means that those compounds may be as a suitable sensitizer for solar energy conversion applications.     

XANES studies of monosubstituted benzhydrazide complexes of copper

K x‐ray absorption near‐edge structure (XANES) studies were carried out on nine samples of monosubstituted benzhydrazide complexes of copper, viz. copper(II) benzhydrazide, o‐, m‐ and p‐hydroxybenzhydrazide, o‐, m‐ and p‐nitrobenzhydrazide and o‐ and p‐chlorobenzhydrazide. These complexes are known for their pharmacological activity as antitubercular agents, antibacterial agents and as fungicides. In the three categories of substituted benzhydrazides the ionicity is found to increase in the order para > meta > ortho. Our studies revealed that the substituted complexes are less ionic than the parent complex. Among the three groups, hydroxy‐substituted complexes are more ionic than nitro‐ and chloro‐substituted hydrazides. Splitting of the principal absorption maximum (1s → 4p) takes place in most of these complexes. The splitting into two components has been assigned to the transitions 1s → A*(4p_z) and 1s → B*(4p_x, 4p_y). The estimated bandgap values for these complexes decrease in the order ortho > meta > para. The present studies indicate that as the chemical shift values increase in all the three groups, the bandgap energy values decrease. Copyright © 2004 John Wiley & Sons, Ltd.