Samarium(III) picrate tetraethylene glycol complex: Photoluminescence study and active material in monolayer electroluminescent

A mononuclear Sm(III) complex involving Pic and EO4 (where Pic=picrate anion and EO4=tetraethylene glycol) has been studied. It shows a bright-orange emission when used as active material in a monolayer electroluminescent device of ITO/EO4-Sm-Pic/Al. The crystal structure of the complex consists of [Sm(Pic)₂(H₂O)(EO4)]⁺ cation and [Pic]⁻ anion. The Sm(III) ion is coordinated with nine oxygen atoms from one EO4 ligand in a pentadentate mode, two Pic anions each in bidentate and monodentate modes, and one water molecule. Both the terminal alcohol groups of the acyclic EO4 ligand were involved in the O-H…O hydrogen bonding by infinite one-dimensional (1D) chain within a symmetry direction [0 1 0]. The photoluminescence (PL) spectrum of the thin film shows the typical spectral features of the Sm(III) ion (⁴G_5/2→⁶H_7/2 transitions). The root-mean-square (rms) of the roughness of thin film is 30.605 nm and indicates that the formation of the monolayer electroluminescent device is not uniform and retains a high crystallinity. Typical semiconductor current-voltage (I-V) property was also observed in this device with threshold and turn voltages of 2.8 and 6.2 V, respectively. The [Sm(Pic)₂(H₂O)(EO4)](Pic)·H₂O complex can be applied as a luminescent center in OLED for bright-orange emission.     

Current transport mechanism and photovoltaic properties of photoelectrochemical cells of ITO/TiO2/PVC–LiClO4/graphite

This paper deals with the current transport mechanism of solid state photoelectrochemical cells of ITO/TiO₂/PVC–LiClO₄/graphite as well as the physical properties of a component of a device affecting its performance. The principle of operation and a schematic energy level diagram for the materials used in the photoelectrochemical cells are presented. The device makes use of ITO films, TiO₂ films, PVC–LiClO₄ and graphite films as photoanode, photovoltaic material, solid electrolyte and counter electrode, respectively. The device shows rectification. The J_sc and V_oc obtained at 100 mW cm⁻² were 0.95 μAcm⁻² and 180 mV, respectively.     

Structural and luminescence studies of trivalent europium complexes with pentaethylene glycol and 18-crown-6 ligands in the presence of picrate anion

Two new isostructural complexes of europium picrate (Eu-Pic) with pentaethylene glycol (EO5) and 18-crown-6 (18C6) ligands formed complexes of molecular formula [Eu(Pic)₂(18C6)]⁺(Pic)⁻I and [Eu(Pic)₂(EO5)]⁺(Pic)⁻II have been isolated and characterised. Compound I showed 10-coordination number through six oxygen atoms from the 18C6 ligand and two bidentate picrate anions. Meanwhile, compound II exhibited 9-coordination number via six oxygen atoms from EO5 ligand, two oxygen atoms from a bidentate and one oxygen atom from monodentate picrate anions. Photoluminescence (PL) spectra of the solid-state europium complexes display sharp lines which are assigned to ⁵D₀→⁷F_0-4 and ⁵D₁→⁷F_1,2,4 transitions. No emission of polyether ligands is observed, indicating that the energy transfer from the polyether ligands to the Eu³⁺ ion is quite efficient. The PL spectra of [Eu(Pic)₂(OH₂)₆]⁺(Pic)⁻·6H₂O III, [Eu(NO₃)₃(OH₂)₃]·(18C6) IV, [Eu(NO₃)₃·6H₂O] V and Eu₂O₃VI are also observed. Compounds I-IV exhibited high Ω₂ intensity parameter values, namely 16.93, 10.23, 17.10 and 12.35 (in units of 10⁻²⁰ cm²), respectively. These relatively high values reflect the hypersensitive behaviour of the ⁵D₀→⁷F₂ transition and indicate that the Eu³⁺ ion is located in a highly polarisable chemical environment.     

High temperature protonic conduction in Sr-doped LaP3O9

Electrical conduction of Sr-doped LaP₃O₉ ([Sr]/{[La] + [Sr]} = 2–10 mol%) was investigated under 0.4–5 kPa of p(H₂O) and 0.01–100 kPa of p(O₂) or 0.3–3 kPa of p(H₂) at 573–973 K. Sr-doped LaP₃O₉ showed apparent H/D isotope effect on conductivity regardless of the Sr-doping level under both H₂O/O₂ oxidizing and H₂/H₂O reducing conditions at investigated temperatures. Conductivities of the material were almost independent of p(O₂) and p(H₂O). These results demonstrated that the Sr-doped LaP₃O₉ exhibited protonic conduction under wide ranges of p(O₂), p(H₂O) and temperature. The conductivity of the Sr-doped LaP₃O₉ increased with increasing Sr concentration up to its solubility limit, ca. 3 mol%, while the further Sr-doping slightly degraded the conductivity. These indicate that Sr²⁺ substitution for La³⁺ leads to proton dissolution into the material and induced protonic conduction. Conductivities of the 3 mol% Sr-doped sample were 2 × 10^- 6–5 × 10^− 4 S cm^− 1 at 573–973 K.     

Structural,vibrational study and superprotonic behavior of a new mixed dipotassium hydrogenselenate dihydrogenphosphate K2(HSeO4)1.5(H2PO4)0.5

Ongoing studies of the KHSeO₄–KH₂PO₄ system aiming at developing novel proton conducting solids resulted in the new compound K₂(HSeO₄)_1.5(H₂PO₄)_0.5 (dipotassium hydrogenselenate dihydrogenphosphate). The crystals were prepared by a slow evaporation of an aqueous solution at room temperature. The structural properties of the crystals were characterized by single-crystal X-ray analysis: K₂(HSeO₄)_1.5(H₂PO₄)_0.5 (denoted KHSeP) crystallizes in the space group P 1¯ with the lattice parameters: a = 7.417(3) Å, b = 7.668(2) Å, c = 7.744(5) Å, α = 71.59(3)°, β = 87.71(4)° and γ = 86.04(6)°. This structure is characterized by HSeO₄⁻ and disordered (H_xSe/P)O₄⁻ tetrahedra connected to dimers via hydrogen bridges. These dimers are linked and stabilized by additional hydrogen bonds (O–H–O) and hydrogen bridges (O–H…O) to build chains of dimers which are parallel to the [0, 1, 0] direction at the position x = 0.5.The differential scanning calorimetry diagram showed two anomalies at 493 and 563 K. These transitions were also characterized by optical birefringence, impedance and modulus spectroscopy techniques. The conductivity relaxation parameters of the proton conductors in this compound were determined in a wide temperature range. The transport properties in this material are assumed to be due to H⁺ protons hopping mechanism.     

Superior performance characteristics for the poly(2,5-dimethoxyaniline)–poly(styrene sulfonic acid)-based electrochromic device

We have fabricated an electrochromic (EC) device with poly(2,5-dimethoxyaniline), PDMA, entrapped in poly(styrene sulfonic acid) (PSS) as an electrochromic layer. The device showed improved performances like stability, optical contrast, etc., over the device with a PDMA layer doped by H₂SO₄. In the process of fabrication of the EC device with a sandwich configuration, indium tin oxide (ITO)/PDMA–PSS||poly(ethyleneimine) (PEI)/orthophosphoric acid (H₃PO₄)/WO₃/ITO, electrochemical polymerization of 2,5-dimethoxyaniline (DMA) was performed with PSS as electrolyte and ITO coated glass as working electrode. The performance characteristics of EC device, like optical contrast, stability, switching time, etc., were followed by cyclic voltammetry, double potential step chronoamperometry and in-situ spectroelectrochemistry. The device was operated in between − 1 V and + 1 V, and absorption characteristics were followed by in-situ UV–visible spectroscopy. A visible contrast in color upon switching the potential from − 1 V to + 1 V was noticed for the device. The device was pale yellow at − 1 V and dark green at + 1 V. Incorporation of PSS into PDMA resulted enhancement in the performance of the complementary electrochromic device. The optical contrast of the device was improved by incorporating PSS into PDMA matrix. The device retained nearly 50% of their optical contrast after 10,000 double steps informing the superior performance of PDMA–PSS in the EC device.     

Detection of OH radical and O atom during triboluminescence of hydrated cerium/terbium sulfates

Triboluminescence of Се₂(SO₄)₃·8H₂O and Tb₂(SO₄)₃·8H₂O crystals has been studied. For the first time spectral evidence for a contribution of light-emitting products OH^? (283 and 290 nm maxima, 1–0 transition; 308.4 and 309.6 nm, 0–0 transition) and excited oxygen atom O^? (777 nm, 3P⁵P—3S⁵S) produced via mechano-chemical decomposition of H₂O and O₂ molecules in the destruction of crystal hydrates of the salts to the gas-phase component of triboluminescence has been obtained.     

Mono(pyridine-N-oxide) analog of DOTA as a suitable organic reagent for a sensitive and selective fluorimetric determination of Ln(III) ions

The mono(pyridine-N-oxide) analog of the H₄dota macrocylic ligand, H₃do3a-py^NO, is capable of forming thermodynamically stable and kinetically inert Ln(III) complexes. Its Eu(III) and Tb(III) complexes display a strong long-lived fluorescence as a result of the antenna effect of the pyridine-N-oxide fluorophore in the reagent. It is shown that H₃do3a-py^NO can be used as a fluorogenic reagent for the determination of Eu(III) and Tb(III) at pH 6.5 and c_L=1 mM. At an excitation wavelength of 286 nm, the emission maxima are 615 nm (Eu(III)-complex), and 547 nm (Tb(III)complex). Detection limits are at concentrations around 1.0 μM and linearity of the method spans over 2 orders of magnitude. The method was applied to artificial and real samples (spiked mineral waters, extracts from cathode ray tube luminophore dust) and gave satisfactory results. The method is simple, rapid, and hardly interfered by other metal ions.     

Line lists for H218O and H217O based on empirical line positions and ab initio intensities

New line lists for isotopically substituted water are presented. Most line positions were calculated from experimentally determined energy levels, while all line intensities were computed using an ab initio dipole moment surface. Transitions for which experimental energy levels are unavailable use calculated line positions. These line lists cover the range 0.05–20 000 cm^?1 and are significantly more complete and potentially more accurate than the line lists available via standard databases. All lines with intensities (scaled by isotopologue abundance) greater than 10^?29 cm/molecule at 296 K are included, augmented by weaker lines originating from pure rotational transitions. The final line lists contain 39 918 lines for H₂¹⁸O and 27 546 for H₂¹⁷O and are presented in standard HITRAN format. The number of experimentally determined H₂¹⁸O and H₂¹⁷O line positions is, respectively, 32 970 (83% of the total) and 17 073 (62%) and in both cases the average estimated uncertainty is 2×10^?4 cm^?1. The number of ab initio line intensities with an estimated uncertainty of 1% is 16 621 (42%) for H₂¹⁸O and 13 159 (48%) for H₂¹⁷O.     

Development of zeolite-derived novel aluminosilicate phosphors

In this research, zeolite-derived aluminosilicate phosphors were synthesized through the ion exchange route. Red light-emitting property of Eu³⁺-doped aluminosilicate phosphors were discussed from a view point of the Eu content, heat-treatment condition and the oxidation state of Eu ions. The crystalline phase of the host aluminosilicates could be successfully controlled as designed based on the published NaAlO₂–SiO₂ binary phase diagram. Orange-red emission peaks derived from the ⁵D₀→⁷F_j (j=0, 1, 2, 3, 4) transition of Eu³⁺ were observed around 590–700 nm, and 4f⁶5d→4f⁷ transition of Eu²⁺ was observed at around 400–500 nm. The relative intensity I(⁵D₀→⁷F₂) of the dominant emission peak at 612 nm increased consistently with the Eu content. The results of the XANES spectroscopy analysis revealed that Eu²⁺ ion in the 1400 °C as heat-treated host aluminosilicate were successfully converted to Eu³⁺ by the additional annealing at 1100 °C. The Eu contents and heat-treatment conditions were determined to exhibit the best performance as a red phosphor, which were 10 wt% and 1500 °C, respectively     

Phase transitions,ferroelectric behavior and second-order nonlinear optics of a new mixed sodium dihydrogen phosphate–arsenate

Aiming at the development of new proton conducting solids, recent studies of the NaH₂PO₄·H₂O–NaH₂AsO₄·H₂O system have lead to the synthesis of a new compound NaH₂(PO₄)_0.48(AsO₄)_0.52·H₂O (NDAP). Calorimetric studies have confirmed the presence of four reversible phase transitions (abbreviated by PhT), at 257/270 (PhT, IV), 261/290 (PhT, III), 267/301 (PhT, II) and 317/317.5 K (PhT, I) (for cooling/heating processes, respectively). It is shown that the III and IV phase transitions are of a first order type, with a “order-disorder and displacive” character, accompanied by specific dielectric anomalies. The behavior of the dielectric constant ε′_r and of tan δ shows that, at 272 K, the (PhT, IV) could be ferroelectric–paraelectric. As for the (PhT, III) at 296 K, it leads to a superionic–protonic phase; a jump in the conductivity is associated to this transition with an unusual high value of conductivity 1.07×10^?4 Ω^?1 cm^?1 and a low activation energy 0.39 eV (Kh. Jarraya et al.). Quandratic nonlinear (NLO) properties of NDAP powder was confirmed efficiency of the grown crystal by the Kurtz and Perry second harmonic generation (SHG) technique.     

Enhanced performance of the OLED with plasma treated ITO and plasma polymerized thiophene buffer layer

In this work, indium-tin-oxide (ITO) electrode in organic light emitting device (OLED) was modified by using an O₂ plasma treatment and plasma polymerized thiophene buffer layers were inserted between ITO (anode) and organic layer in order to improve the hole injection efficiency. Furthermore, electron injection to cathode (Al) in the test OLED seemed to be improved due to introduction of quantum well in the cathode. The plasma-polymerized thiophene buffer layer on the O₂ plasma-treated transparent ITO electrode seemed to result in formation of a stable interface and consequently, reduction the hole mobility, which in turn caused enhanced recombination of hole and electron in the emitting layer. Compared with the test device without buffer layer, the turn-on voltage of the test device with the buffer layer was lowered by 1.0 V.     

Red organic light-emitting diodes with high efficiency,low driving voltage and saturated red color realized via two step energy transfer based on ADN and Alq3 co-host system

We demonstrated efficient red organic light-emitting diodes based on a wide band gap material 9,10-bis(2-naphthyl)anthracene (ADN) doped with 4-(dicyano-methylene)-2-t-butyle-6-(1,1,7,7-tetramethyl-julolidyl-9-enyl)-4H-pyran (DCJTB) as a red dopant and 2,3,6,7-tetrahydro-1,1,7,7,-tetramethyl-1H,5H,11H-10(2-benzothiazolyl)quinolizine-[9,9a,1gh]coumarin (C545T) as an assistant dopant. The typical device structure was glass substrate/ITO/4,4′,4″-tris(N-3-methylphenyl-N-phenyl-amino)triphenylamine (m-MTDATA)/N,N′-bis(naphthalene-1-yl)-N,N′-diphenyl-benzidine (NPB)/[ADN:Alq₃]:DCJTB:C545T/Alq₃/LiF/Al. It was found that C545T dopant did not by itself emit but did assist the energy transfer from the host (ADN) to the red emitting dopant via cascade energy transfer mechanism. The OLEDs realized by this approach significantly improved the EL efficiency. We achieved a significant improvement regarding saturated red color when a polar co-host emitter (Alq₃) was incorporated in the matrix of [ADN:Alq₃]. Since ADN possesses a considerable high electron mobility of 3.1 × 10⁻⁴ cm²  V⁻¹ s⁻¹, co-host devices with high concentration of ADN (>70%) exhibited low driving voltage and high current efficiency as compared to the devices without ADN. We obtained a device with a current efficiency of 3.6 cd/A, Commission International d’Eclairage coordinates of [0.618, 0.373] and peak λ_max = 620 nm at a current density of 20 mA/cm². This is a promising way of utilizing wide band gap material as the host to make red OLEDs, which will be useful in improving the electroluminescent performance of devices and simplifying the process of fabricating full color OLEDs.     

Resourceful synthesis of pyrazolo[1,5-a]pyrimidines under ultrasound irradiation

Pyrazolo[1,5-a]pyrimidines were synthesized via the ultrasonic sonochemical method using the cyclocondensation reaction of 4-alkoxy-1,1,1-trifluoro-3-alken-2-ones [CF₃C(O)CH = C(R)(OMe) – where R = Me, Bu, i-Bu, Ph, 4-Me–C₆H₄, 4-F–C₆H₄, 4-Cl–C₆H₄, 4-Br–C₆H₄, naphth-2-yl and biphen-4-yl] – with 3-amino-5-methyl-1H-pyrazole in the presence of EtOH for 5 min. This methodology has several advantages, for example, it is a simple procedure, it has an easy work-up, mild conditions, short reaction times (5 min) and produces satisfactory yields (61–98%).     

Synthesis,crystal structure,spectroscopic characterization and optical properties of bis(4-acetylanilinium) tetrachlorocobalt (II)

The chemical preparation, crystal structure, spectroscopic investigations and optical features are given for a novel organic–inorganic hybrid material [C₈H₁₀NO]₂CoCl₄.The compound is crystallized in the orthorhombic space group Cmca, with the following unit cell parameters: a=19.461(2) Å, b=15.523(2) Å, c=13.7436(15) Å, and Z=8. The atomic arrangement shows an alternation of organic and inorganic layers along the b-axis. The cohesion between these entities is performed by N–H…Cl and N–H…O hydrogen bonds and π–π stacking interactions.Infrared and Raman spectra at room temperature are recorded in the 4000−400 and 4000−0 cm⁻¹ frequency regions, respectively and analyzed on the basis of literature data. This study confirms the presence of the organic cation [C₈H₁₀NO]⁺ and of the [CoCl₄]²⁻ anion. UV–vis spectroscopy results showed the indirect transition with band gap energy 2.98 eV.     

Electrical characteristics and efficiency of organic light-emitting diodes depending on hole-injection layer

In a device structure of ITO/hole-injection layer/N,N′-biphenyl-N,N′-bis-(1-naphenyl)-[1,1′-biphthyl]4,4′-diamine(NPB)/tris(8-hydroxyquinoline)aluminum(Alq₃)/Al, we investigated the effect of the hole-injection layer on the electrical characteristics and external quantum efficiency of organic light-emitting diodes. Thermal evaporation was performed to make a thickness of NPB layer with a rate of 0.5–1.0 Å/s at a base pressure of 5 × 10⁻⁶ Torr. We measured current–voltage characteristics and external quantum efficiency with a thickness variation of the hole-injection layer. CuPc and PVK buffer layers improve the performance of the device in several aspects, such as good mechanical junction, reducing the operating voltage, and energy band adjustment. Compared with devices without a hole-injection layer, we found that the optimal thickness of NPB was 20 nm in the device structure of ITO/NPB/Alq₃/Al. By using a CuPc or PVK buffer layer, the external quantum efficiencies of the devices were improved by 28.9% and 51.3%, respectively.     

Crystal growth and characterization of a new co-ordination complex—barium tetrakis(maleate) dihydrate

Crystals of barium tetrakis(maleate) dihydrate [Ba₄(C₄H₂O₄)₄]^?2H₂O are grown in gelated hydrosilica matrix. Single crystal X-ray diffraction studies show that the crystal system is monoclinic with space group P2₁/c. The unit cell dimensions are a=9.3721(2)  Å, b=20.5880(7)  Å, c=14.0744(4) Å, α=γ=90°, β=90.289(2)°. Powder XRD studies confirmed the single phase nature of the grown crystals. The FTIR data is in conformity with the XRD results. The TG–DTA curves of the material indicate a three-step thermal decomposition. The response of the dielectric properties in the temperature range 30 °C to 500 °C is correlated with the TG–DTA results.     

Infrared spectra of acetylene–water complexes: C2D2–H2O,C2D2–HDO,and C2D2–D2O

Infrared spectra of C₂D₂–water complexes are studied in the 4.1 μm region of the C₂D₂ ν₃ fundamental band using a tunable diode laser source to probe a pulsed supersonic slit jet. Relatively large vibrational red shifts (?27.7 to ?28.0 cm^?1) are observed which are more easily interpretable than for the analogous C₂H₂ vibration thanks to the absence of Fermi resonance effects for C₂D₂. Noticeable homogeneous line broadening leads to estimates of upper state predissociation lifetimes of about 0.5, 0.9 and 1.1 ns for C₂D₂–H₂O, –HDO, and –D₂O, respectively. Transitions involving K_a = 0 and 1 levels are observed for C₂D₂–HDO, but there is a puzzling absence of K_a = 1 for C₂D₂–H₂O and C₂D₂–D₂O.     

Electrochemical characterization on layered lithium ruthenate for electrochemical supercapacitors

Electrochemical characteristics of lithium ruthenate (Li_xRuO_2+0.5x·nH₂O) for electrochemical capacitors' electrode material were first examined in this paper by cyclic voltammetry, electrochemical impedance spectroscopy and galvanostatic charge–discharge tests. Results show that Li_xRuO_2+0.5x·nH₂O has electrochemical capacitive characteristic within the potential range of − 0.2–0.9 V (vs. SCE) in 1 M Li₂SO₄ solution. The capacitance mainly arises from pseudo-capacitance caused by lithium ions' insertion/extraction into/out of the Li_xRuO_2+0.5x·nH₂O electrode. The specific capacitance of 391 F g^− 1 can be delivered at 1 mA charge–discharge current for Li_xRuO_2+0.5x·nH₂O electrode with an energy density of 65.7 W h kg^− 1. This material also exhibits an excellent cycling performance and there is no attenuation of capacitance over 600 cycles.     

Chemical diffusion of water in the double perovskites Ba4Ca2Nb2O11 and Sr6Ta2O11

The mechanism and kinetics of water incorporation in the double perovskites Ва₄Ca₂Nb₂O₁₁ and Sr₆Ta₂O₁₁ has been investigated (T = 300÷500 °C and aH₂O = 1 · 10^− 3÷2.2 · 10^− 2). The formation of hydration products Ba₄Ca₂Nb₂O₁₁·xH₂O and Sr₆Ta₂O₁₁·xH₂O (0.2 < x < 0.50) was limited by the diffusion of H₂O. It has been found that the concentration dependences of D˜_H2O are the same for both samples: small increasing of D˜_H2O with increasing x. The temperature dependences of the chemical diffusion coefficients of water for compositions of Ba₄Ca₂Nb₂O₁₁·0.35H₂O and Sr₆Ta₂O₁₁·0.35H₂O could be described with close activation energies of E_a = 0.38 ± 0.03 eV and E_a = 0.49 ± 0.03 eV, respectively. The chemical diffusion coefficients of water are nearly one order of magnitude smaller for tantalate Sr₆Ta₂O₁₁. This result correlates with lower oxygen and proton conductivities in Sr₆Ta₂O₁₁ as the consequence of lower mobilities.