Synthesis, structure, electrochemistry, photophysics and electroluminescence of 1,3,4-oxadiazole-based ortho-metalated iridium(III) complexes

Four new iridium(III) complexes 1-4, with 1,3,4-oxadiazole derivative as cyclometalated ligand for the first time, have been synthesized and structurally characterized by NMR, EA, MS and X-ray diffraction analysis (except 1). The stronger ligand field strength of the dithiolate ancillary ligands results in higher oxidation potentials and lower HOMO energy levels of complexes than acetylacetone. The absorption spectra of these complexes display low-energy metal-to-ligand charge transfer transition ranging from 350 to 500 nm. Complexes with dithiolate ancillary ligand emit at maximum wavelengths of ca. 500 nm, blue shifting 17 and 11 nm with respect to their counterpart with acetylacetone ligand. The electrophosphorescent devices with 2-4 as phosphorescent dopant in emitting layer have been fabricated. All devices have a low turn-on voltage in the range of 4.5 and 4.9 V. A high-efficiency green emission with maximum luminous efficiency of 5.28 cd/A at current density of 1.37 mA/cm(2) and a maximum brightness of 2592 cd/m(2) at 15.2 V has been achieved in device using 2 as emitter.

Kinetic and electrochemical properties of icosahedral quasicrystalline Ti45Zr35Ni17Cu3 powder

Kinetic and electrochemical properties of icosahedral quasicrystalline Ti45Zr35Ni17Cu3 alloy powder as negative electrode material of Ni-MH battery have been investigated at different temperatures. The calculated results show that the apparent activation enthalpy of the charge-transfer reaction is 43.89 kJ mol(-1), and the activation energy of hydrogen diffusion is 21.03 kJ mol(-1). The exchange current density and the diffusion coefficient of hydrogen in the bulky electrode increase with increasing temperature, indicating that increasing temperature is beneficial to charge-transfer reaction and hydrogen diffusion. As a result, the maximum discharge capacity, activation property and high-rate dischargeability are greatly improved with increasing temperature. However, the charge retention and the cycling stability degrade with the increase of the temperature.

Synthesis and characterization of spherical Sr2CeO4 phosphors by spray pyrolysis for field emission displays

A blue emitting Sr2CeO4 phosphor with a one-dimensional structure has been prepared by a two-step spray pyrolysis (SP) method, starting from the aqueous solutions of metal nitrates with citric acid and polyethylene glycol (PEG) as additives. The material is ultimately designed for field emission displays (FEDs). X-ray diffraction (XRD), thermogravimetric and differential thermal analysis (TG-DTA), field emission scanning electron microscope pictures (FE-SEM) as well as photoluminescence (PL) and cathodoluminescence (CL) spectroscopy and lifetime measurements have been employed to characterize the samples. The morphology, PL and low voltage CL properties of Sr2CeO4 phosphors as-prepared using the SP method have been investigated by changing the concentration of the precursor solution, concentration of PEG, annealing temperature, acceleration voltage and filament current. The obtained Sr2CeO4 phosphor particles are spherical and of submicron size, 0.5-2 mu m. The emission spectrum of the phosphors shows a broad band with maximum at 467 nm (lifetime = 37.4 mu s; CIE chromaticity coordinates: x = 0.15 and y = 0.21), presumably due to a ligand-to-metal charge-transfer transition.

VIV-UV excited luminescent properties of LnCa4O(BO3)3 : RE3+(Ln = Y, La, Gd; Re=Eu, Tb, Dy, Ce)

Calcium lanthanide oxyborate doped with rare-earth ions LnCa(4)O(BO3)(3):RE3+ (LnCOB:RE, Ln = Y, La, Gd, RE = Eu, Tb, Dy, Cc) was synthesized by the method of solid-state reaction at high temperature. Their fluorescent spectra were measured from vacuum ultraviolet (VUV) to visible region at room temperature. Their excitation spectra all have a broadband center at about 188 nm, which is ascribed to host absorption. Using Dorenbos' and J phi rgensen's work [P. Dorenbos, J. Lumin. 91 (2000) 91, R. Resfeld, C.K. J phi rgensen. Lasers and Excite States of Rare Earth [M], Springer, Berlin, 1977, p. 45], the position of the lowest 5d levels E(Ln,A) and charge transfer band E-ct were calculated and compared with their excitation spectra.Eu3+ and Tb3+ ions doped into LnCOB show efficient luminescence under VUV and UV irradiation. In this system, Ce3+ ions do not show efficient luminescence and quench the luminescence of Tb3+ ions when Tb3+ and Ce3+ ions are co-doped into LnCOB. GdCOB doped with Dy3+ shows yellowish white light under irradiation of 254 nm light for the reason that Gd ions transfer the energy from itself to Dy.

Electrochemical properties of Ti0.17Zr0.08V0.35Cr0.10Ni0.30 alloy electrode

The electrochemical properties of the Ti0.17Zr0.08V0.35Cr0.10Ni0.30 alloy electrode were investigated. This alloy has good cycle life at 303 K, 313 K, and even at 323 K, but the discharge capacity decreases gradually at 333 K with increasing cycle number. Both the charge-discharge efficiency and the charge-discharge voltage reduce. The electrochemical impendence spectra indicate that the charge-transfer resistance decreases while the exchange current density increases as temperature increases. The apparent activation energy of the charge-transfer reaction is about 50 kJ mol(-1), which is higher than that on the AB(5) type alloy electrode.

Synthesis, characterization, photoluminescent and electroluminescent properties of new conjugated 2,2 '-(arylenedivinylene)bis-8-substituted quinolines

A series of new PPV oligomers containing 8-substituted quinoline, 2,2'-(arylenedivinylene) bis-8-quinoline derivatives, were designed and synthesized via a Knoevenagel condensation reaction of quinaldine, 8-hydroxy-or 8-methoxy-quinaldine with aromatic dialdehydes. These PPV oligomers were characterized by H-1 and C-13-NMR, X-ray diffraction, elemental analysis, UV-visible and fluorescence spectroscopies. The X-ray diffraction investigation showed that there are intermolecular pi...pi interactions in the solid state in 1 and 3. The optical and photoluminescent properties study demonstrated that the emission color of the resulting materials varies from blue to yellow and is dependent on the substituents (pi-donor and pi-acceptor groups) on both sides of the conjugated molecules and the aromatic core in the middle of the conjugated backbones. The electroluminescent devices using compounds 1-4 as the emitters and electron-transporting layers were fabricated with the structure ITO/NPB/emitter/LiF/Al. The best device performance with the maximum brightness of 5530 cd m(-2) and the luminous efficiency of 2.4 cd A(-1) is achieved by using compound 4, with intramolecular charge transfer character, as the emitter; these values represent a more than 5-fold improvement in brightness and efficiency compared to compound 3 without methoxy groups on the phenyl rings.

VUV-UV excited luminescent properties of calcium borophosphate doped with rare earth ions

The VUV-UV spectra of rare earth ions activated calcium borophosphate, CaBPO5:RE (RE = Ce3+, sm(3+), Eu2+, Eu3+, Tb3+ and Dy3+) were determined. The bands at about 155 nm in the VUV excitation spectra are attributed to the host lattice absorptions. The bands at 166 and 190 nm for the sample CaBPO5:Sm have been considered as related to the f-d transition and the charge transfer band (CTB) of Sm3+ ions, and the band at 169 nm for the sample CaBPO5:Dy is assumed to be connected with the f-d transition of the Dy3+ ions in CaBPO5. The partial reduction of Eu3+ CaBPO5:Eu prepared by high temperature solid state reaction in air is confirmed by the VUV-UV spectra.

VUV-UV photoluminescence spectra of strontium orthophosphate doped with rare earth ions

The measurements of VUV-UV photoluminescence emission (PL) and photoluminescence excitation (PLE) spectra of rare earth ions activated strontium orthophosphate [Sr-3(PO4)(2):RE, RE = Ce, Sm, Eu, Tb] are performed. Whenever the samples are excited by VUV or UV light, the typical emission of Ce-3+,Ce- Sm3+, Eu3+, Eu2+ and Tb3+ ions can be observed in PL spectra, respectively. The charge transfer bands (CTBs) of Sm3+ and Eu3+ are found, respectively, peaking at 206 and 230nm. The absorption bands peaking in the region of 150-160 nm are assigned to the host lattice sensitization bands, i.e., the band-to-band transitions of PO43- grouping in Sr-3(PO4)(2). It is speculated that the first f-d transitions of Sm3+ (Eu3+), and the CTB of Tb3+ are, respectively, located around 165 (14 3) and 167 urn by means of VUV-UV PLE spectra and relational empirical formula, these f-d transitions or CT bands are included in the bands with the maxima at 150-160 nm, respectively. The valence change of europium from trivalent to divalent in strontium orthophosphate prepared in air is observe by VUV-UV PL and PLE spectra.

Vacuum ultraviolet optical properties of (La,Gd)PO4 : RE3+ (RE = Eu, Tb)

Vacuum ultraviolet excitation spectra of phosphors (La,Gd)PO4:RE3+ (RE = Eu or Tb) and X-ray photoelectron spectra of LaPO4 and GdPO4 are investigated. The vacuum ultraviolet excitation intensity of (La,Gd)PO4:RE3+ is enhanced with the increasing of Gd3+ content, which implies that Gd3+ plays an intermediate role in energy transfer from host absorption band to RE3+. When Gd3+ is doped into LaPO4:Eu, charge transfer band (CT band) begins to shift to higher energy region and the overlap degree of CT band and the host absorption band gets greater with more Gd3+ doped into LaPO4. These results suggest that the dopant (Gd3+) gives an important influence on energy transfer efficiency. The top of LaPO4 valance band is formed by the 2p level of O2-, whereas that of GdPO4 valance band is formed by the 2p level of O2- and the 4f level of Gd3+, showing the differences in band structures between LaPO4 and GdPO4.

Preparation of Y3Al5O12 : Eu phosphors by citric-gel method and their luminescent properties

By using metal nitrates as starting materials and citric acid as complexing agent, Y3Al5O12 (YAG) and Y3Al5O12:Eu (1 mol%) (YAG:Eu) powder phosphors were prepared by a citrate-gel method. The formation process of YAG and YAG:Eu were investigated by means of XRD, TG-DTA and FT-IR spectra. The purified crystalline phases of YAG and YAG:Eu were obtained at 800 degreesC. The crystalline YAG:Eu phosphors showed an orange-red emission with D-5(0)-F-7(1) (591 nm) as the most prominent group, whose intensity was dependent on the pH value of the starting solution, citric acid content and firing temperature. It has been found that the suitable pH and citric acid/metal ratio are 3 and 2 for obtaining the highest emission intensity, respectively. The emission intensity increases steadily with increasing the annealing temperature from 800 to 1200 degreesC, and nearly remains constant after 1200 degreesC. Furthermore, great differences were observed for the lifetimes and the charge transfer band of Eu3+ in crystalline and amorphous states of YAG.

Hydrothermal synthesis and crystal structure of a hybrid material based on [Co-4(phen)(8)(H2O)(2)(HPO3)(2)](4+) and a highly reduced polyoxoanion

An unusual composite hybrid material [Co-4 (phen)(8) (H2O)(2) (HPO3)(2)](H3O)(3) [PMo8VI V-4(IV) O-40 ((VO)-O-IV) 2] 1 (phen = 1,10-phenanthroline) has been hydrothermally synthesized from a mixture of NH4VO3, Na2MoO4.2H(2)O, CoCl2.6H(2)O, phen, H3PO3 and water. It was characterized by elemental analysis, IR, UV-vis, XPS, EPR, TG and single crystal X-ray diffraction. The title compound is constructed from the organic-inorganic hybrid [Co-4(phen)(8)(H2O)(2) (HPO3)(2)](4+) and highly reduced bi-capped pseudo-Keggin [(PMo8V4O40)-V-VI-O-IV ((VO)-O-IV)(2)](7-) polyoxoanions The structure exhibits an extended 2D network through hydrogen bonds among cations, anions and H2O, combining polyoxometalates with metal phosphonates for the first time.

Formation of a supported hybrid bilayer membrane on gold: A sterically enhanced hydrophobic effect

Adsorption of a monolayer of didecanoyl-L-alpha-phosphatidylcholine (DDPC) from dispersions of small unilamellar vesicles onto hydrophobic surfaces was investigated by mean of cyclic voltammetry and impedance spectroscopy. The hydrophobic surfaces were self-assembled monolayers of 2-mereapto-3-n-octylthiophene (MOT) on gold. One characteristic of the MOT monolayer is its permeability to organic molecules in aqueous solution, thus providing a more energetically favorable hydrophobic surface for the addition of phospholipid vesicles. The kinetics of the lipid monolayer formation were followed by measuring the time-dependent interfacial capacitance. Unusual values of thickness and capacitance of the MOT/ DDPC bilayers were observed. An interdigitating conformation of the bilayer structure was proposed to interpret the experimental results, The horseradish peroxidase reconstituted into the bilayer demonstrated the expected protein activity, showing practical use in research and in biosensor application.

VUV and Eu-L-3 edge XANES spectra of europium-doped strontium tetraborate prepared in air

VUV-UV and Eu-L-3 edge XANES spectra were measured for europium-doped strontium tetraborate prepared by solid state reaction at high temperature in air. The VUV-UV spectra show that the host absorption band of (SrBO7)-O-4 appears below 170 nm. The charge transfer band of Eu3+ doped in SrB4O7 is peaked at 272 nm. The 4f-5d transitions of Eu2+ consist of a band peaked at 310 nm with a shoulder at 280 nm and also include the bands peaked at 238 (weak) and 203 (strong) nm. The result of XANES spectrum at Eu-L3 edge of the synthesized sample indicates that Eu3+ and Eu2+ coexist in SrB4O7:Eu prepared in air, which is consistent with the results of the VUV-UV spectra.

Aggregation behavior of amphiphilic D-pi-A molecules bearing recognition group

Aggregation behavior of two amphiphilic D-pi -A molecules bearing barbituric acid as both recogniton group and electron-drawing substituent, 5-(4-dodecyl oxybenzylidene)-(1H, 3H)-2,4,6-pyrimidine trione (PB12) and 5-(4-N,N-didodecyl aminobenzylidene)-(1H,3H)-2,4,6-pyrimidine trione (AB(12)) was studied by UV-visible, fluorescence, and surface voltaic spectroscopies (SPS). The experimental results indicate that PB12 tends to form J-aggregate and AB(12) tends to form H-aggregate under increasing concentration. An intramolecular twisted charge transfer (TICT) emission around 500 nm is observed when J-aggregate is formed between PB12 molecules, and an excimer emission around 600 nm is observed when H-aggregate is formed between AB(12) molecules.