Highly efficient electroluminescence from green-light-emitting electrochemical cells based on Cu-I complexes

The complexes [Cu(dnpb)(DPEphos)](+)(X-) (dnpb and DPEphos are 2,9-di-n-butyl-1,10-phenanthroline and bis[2-(diphenyl-phosphino)phenyl]ether, respectively, and X- is BF4-, ClO4-, or PF6-) can form high quality films with photoluminescence quantum yields of up to 71 +/- 7%. Their electroluminescent properties are studied using the device-structure indium tin oxide (ITO)/complex/metal cathiode. The devices emit green light efficiently, with an emission maximum of 523 nm, and work in the mode of light-emitting electrochemical cells. The response time of the devices greatly depends on the driving voltage, the counterions, and the thickness of the complex film. After pre-biasing at 25 V for 40 s, the devices turn on instantly, with a turn-on voltage of ca. 2.9 V. A current efficiency of 56 cd A(-1) and an external quantum efficiency of 16% are realised with Al as the cathode. Using a low-work-function metal as the cathode can significantly enhance the brightness of the device almost without affecting the turn-on voltage and current efficiency. With a Ca cathode, a brightness of 150 cd m(-2) at 6 V and 4100 cd m(-2) at 25 V is demonstrated. The electroluminescent performance of these types of complexes is among the best so far for transition metal complexes with counterions.

Preparation of highly conductive, self-assembled gold/polyaniline nanocables and polyaniline nanotubes

One-dimensional gold/polyaniline (Au/PANI-CSA) coaxial nanocables with an average diameter of 5060 nm and lengths of more than 1 mu m were successfully synthesized by reacting aniline monomer with chlorauric acid (HAuCl4) through a self-assembly process in the presence Of D-camphor-10-sulfonic acid (CSA), which acts as both a dopant and surfactant. It was found that the formation probability and the size of the Au/PANI-CSA nanocables depends on the molar ratio of aniline to HAuCl4 and the concentration of CSA, respectively. A synergistic growth mechanism was proposed to interpret the formation of the Au/PANI-CSA nanocables. The directly measured conductivity of a single gold/polyaniline nanocable was found to be high (approximate to 77.2S cm(-1)). Hollow PANI-CSA nanotubes, with an average diameter of 50-60 nm, were also obtained successfully by dissolving the Au nanowire core of the Au/PANI-CSA nanocables.

Highly enhanced luminescence from single-crystalline C-60 center dot 1m-xylene nanorods

Single-crystalline C-60 center dot 1m-xylene nanorods with a hexagonal structure were successfully synthesized by evaporating a C-60 solution in m-xylene at room temperature. The ratio of the length to the diameter of the nanorods can be controlled in the range of approximate to 10 to over 1000 for different applications. The photoluminescence (PL) intensity of the nanorods is about 2 orders of magnitude higher than that for pristine C-60 crystals in air. Both UV and Raman results indicate that there is no charge transfer between C-60 and m-xylene. It was found that the interaction between C-60 and m-xylene molecules is of the van der Waals type. This interaction reduces the icosahedral symmetry of C-60 molecule and induces strong PL from the solvate nanorods.

Novel highly stable semiconductors based on phenanthrene for organic field-effect transistors

Two novel phenanthrene-based conjugated oligomers were synthesized and used as p-channel semiconductors in field-effect transistors; they exhibit high mobility and excellent stability during long-time ambient storage and under UV irradiation.

Blue light-emitting polymer with polyfluorene as the host and highly fluorescent 4-dimethylamino-1,8-naphthalimide as the dopant in the sidechain

The dopant/host concept, which is an efficient approach to enhance the electroluminescence (EL) efficiency and stability for organic light-emitting diodes (OLEDs) devices, has been applied to design efficient and stable blue light-emitting polymers. By covalently attaching 0.2 mol % highly fluorescent 4-dimethylamino-1,8-naphthalimide (DMAN) unit (photoluminescence quantum efficiency: Phi(PL)=0.84) to the pendant chain of polyfluorene, an efficient and colorfast blue light-emitting polymer with a dopant/host system and a molecular dispersion feature was developed. The single-layer device (indium tin oxide/PEDOT/polymer/Ca/Al) exhibited the maximum luminance efficiency of 6.85 cd/A and maximum power efficiency of 5.38 lm/W with the CIE coordinates of (0.15, 0.19). Moreover, no undesired long-wavelength green emission was observed in the EL spectra when the device was thermal annealed in air at 180 degrees C for 1 h before cathode deposition. These significant improvements in both efficiency and color stability are due to the charge trapping and energy transfer from polyfluorene host to highly fluorescent DMAN dopant in the molecular level.

Highly efficient green light emitting polyfluorene incorporated with 4-diphenylamino-1,8-naphthalimide as green dopant

The dopant/host methodology, which enables efficient tuning of emission color and enhancement of the electroluminescence (EL) efficiency of organic light emitting diodes (OLEDs) based on small molecules, is applied to the design and synthesis of highly efficient green light emitting polymers. Highly efficient green light emitting polymers were obtained by covalently attaching just 0.3-1.0 mol% of a green dopant, 4-(N,N-diphenyl) amino-1,8-naphthaliniide (DPAN), to the pendant chain of polyfluorene (the host). The polymers emit green light and exhibit a high photoluminescence (PL) quantum yield of Lip to 0.96 in solid films, which is attributed to the energy transfer from the polyfluorene host to the DPAN dopant unit. Single layer devices (device configuration: ITO/PEDOT/Polymer/Ca/Al) of the polymers exhibit a turn on voltage of 4.8 V, luminance efficiency of 7.43 cd A(-1), power efficiency of 2.96 lm W-1 and CIE coordinates at (0.26, 0.58). The good device performance can be attributed to the energy transfer and charge trapping from the polyfluorene host to the DPAN dopant unit as well as the molecular dispersion of the dopant in the host.

Facile sonochemical synthesis of CePO4 : Tb/LaPO4 core/shell nanorods with highly improved photoluminescent properties

A simple, efficient and quick method has been established for the synthesis of CePO4:Tb nanorods and CePO4:Tb/LaPO4 core/shell nanorods via ultrasound irradiation of inorganic salt aqueous solution under ambient conditions for 2 h. The as-prepared products were characterized by means of powder x-ray diffraction (PXRD), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), selected area electron diffraction ( SAED), x-ray photoelectron spectroscopy (XPS), photoluminescence (PL) spectra and lifetimes. TEM micrographs show that all of the as-prepared cerium phosphate products have rod-like shape, and have a relatively high degree of crystallinity and uniformity. HRTEM micrographs and SAED results prove that these nanorods are single crystalline in nature. The emission intensity and lifetime of the CePO4:Tb/LaPO4 core/shell nanorods increased significantly with respect to those of CePO4: Tb core nanorods under the same conditions. A substantial reduction in reaction time as well as reaction temperature is observed compared with the hydrothermal process.

Synthesis of highly faceted multiply twinned gold nanocrystals stabilized by polyoxometalates

A novel and facile chemical synthesis of highly faceted multiply twinned gold nanocrystals is reported. The gold nanocrystals are hexagonal in transmission electron microscopy and icosahedral in scanning electron microscopy. Phosphotungstic acid (PTA), which was previously reduced, serves as a reductant and stabilizer for the synthesis of gold nanocrystals. The PTA-gold nanocomposites are quite stable in aqueous solutions, and electrochemically active towards the hydrogen evolution reaction.

Novel highly active binuclear neutral nickel and palladium complexes as precatalysts for norbornene polymerization

A series of binuclear neutral nickel and palladium complexes [(XC6H2CH=NC6H3-iPr(2))MRL](2) 4b-f (X=NO2, M=Ni, R=Ph, L=PPh3, 4b; X=H, M=Pd, R=Me, L=PPh3,4c; X=H,M=Pd, R=Me, L=Py, 4d; X=NO2,M=Pd, R=Me, L=PPh3, 4e; X=NO2, M=Pd, R=Me, L=Py, 4f) and [(C10H7CH=NC6H3-iPr(2))MRL](2) 8a-c (M=Ni, R=Ph, L=PPh3, 8a; M=Pd, R=Me, L=PPh3, 8b; M=Pd, R=Me, L=Py, 8c) have been synthesized and characterized. The structures of complexes 4e and 8b have also been confirmed by X-ray crystallographic analysis. With modified methylalummoxane (MMAO) as cocatalysts, these complexes and complex [(C6H3CH=NC6H3-iPr(2))NiPh(PPh3)](2) 4a are capable of catalyzing the addition polymerization of norbomene (NBE) with the high activity up to 2.3 x 10(8) g PNBE/(mol(M) h). The structure of complexes affects considerably catalytic activity towards norbomene polymerization. The polymers obtained with nickel complexes are soluble, while those obtained with palladium complexes are insoluble. Palladium complexes 4c, 4e and 8b bearing PPh3 ligands exhibit much higher activities than the corresponding complexes 4d, M and 8c bearing pyridine ligands under the same conditions.

Highly active, hexabutylguanidinium salt/zinc bromide binary catalyst for the coupling reaction of carbon dioxide and epoxides

An experimentally simple and inexpensive catalyst system based on hexabutylguanidinium/ZnBr, has been developed for the coupling of carbon dioxide and epoxides to form cyclic carbonates with significant catalytic activity under mild reaction conditions without using additional organic solvents (e.g. the turnover frequencies (TOF, h(-1)) values as high as 6.6 x 10(3) h(-1) for styrene oxide and 1.01 x 10(4) h(-1) for epichlorohydrin). This catalyst system also offers the advantages of recyclability and reusability. Therefore, it is a very effective, environmentally benign, and simple catalytic process. The special steric and electrophilic characteristics of hexabutylguanidinium bromide ionic liquid result in the prominent performance of this novel catalyst system.

Highly sensitive electrogenerated chemiluminescence produced at Ru(bpy)(3)(2+) in Eastman-AQ55D-carbon nanotube composite film electrode

The electrochemistry and electrogenerated chemilurninescence (ECL) of tris(2,2-bipyridyl)ruthenium(II) ion-exchanged in Eastman-AQ-carbon nanotube (CNT) composite films were investigated at a glassy carbon (GC) electrode. Eastman-AQ55D is a poly (ester sulfonic acid) cation exchanger available in a commercial dissolved form. It is much more hydrophilic than Nafion due to its unique structure, so Ru(bpy)(3)(2+) does not diffuse into the hydrophobic region where it may lose its electroactivity as that in Nafion. The interfused CNT could act as electronic wires that connect the electrode with Ru(bpy)(3)(2+), which made the composite film much more electronically which finally led to the increasing of Ru(bpy)(3)(2+) conductive. Besides, the negatively charged CNT could also absorb some Ru(bpy)(3)(2+). Moreover, the strong electrostatic interaction between AQ and Ru(bpy)(3)(2+) made the composite films much more stable. The combination of AQ and CNT brings excellent sensitivity with the detection limit as low as 3 x 10(-11) M for TPA.

Highly efficient iridium(III) complexes with diphenylquinoline ligands for organic light-emitting diodes: Synthesis and effect of fluorinated substitutes on electrochemistry, photophysics and electroluminescence

A series of novel cyclometalated iridium(III) complexes bearing 2,4-diphenylquinoline ligands with fluorinated substituent were prepared and characterized by elemental analysis, NMR and mass spectroscopy. The cyclic voltammetry, absorption, emission and electroluminescent properties of these complexes were systematically investigated. Electrochemical studies showed that the oxidation of the fluorinated complexes occurred at more positive potentials (in the range 0.57-0.69 V) than the unfluorinated complex 1 (0.42 V). In view of the energy level, the lowering of the LUMO by fluorination is significantly less than that of the HOMO. The weak and low energies absorption bands in the range of 300-600 nm are well resolved, likely associated with MLCT and (3)pi-pi* transitions. These complexes show strong orange red emission both in the solution and solid state. The emission maxima of the fluorinated complexes showed blue shift by 9, 24 and 15 nm for 2, 3 and 4, respectively, with respect to the unfluorinated analogous 1. Multilayered organic light-emitting diodes (OLEDs) were fabricated by using the complexes as dopant materials. Significantly higher performance and lower turn-on voltage were achieved using the fluorinated complexes as the emitter than that using the unfluorinated counterpart 1 under the same doping level.

Highly efficient red electroluminescence induced by efficient electron injection and exciton confinement

HigWy efficient DCJTB-doped device was realized by enhanced electron injection and exciton confinement. A fluorine end-capped linear phenylene/oxadiazole oligomer 2,5-bis(4-fluorobiphenyl-4'-yl)-1,3,4-oxadiazole (1) and a trifluoromethyl end-capped oligomer 2,5-bis(4-trifluoromethylbiphenyl-4'-yl)-1,3,4-oxadiazole (2) were designed and incorporated as an electron transporting/hole blocking material in the device structure ITO/NPB (60 mn)/DCJTB:Alq(3) (0.5%, 10 nm)/1 or 2 (20 nm)/Alq(3) (30 mn)/LiF (1 nm)/Al (100 nm). The devices showed highly efficient red luminescence. In particular, the device based on 1 achieved pure red luminescence at 620 run originating from DCJTB, with a narrow FWHI of 65 nm, maximal brightness of 13,300 cd/m(2) at voltage of 20.8 V and current density of ca. 355 mA/cm(2). High current and power efficiencies (> 3.6 cd/A. 1.01m/W) were retained within a wide range of current densities. Our results show efficient and stable DCJTB-doped red electroluminescence could be anticipated for practical applications by taking advantage of the present approaches. The control experiments using BCP were also studied.

Highly efficient red electroluminescence from stacked organic light-emitting devices based on a europium complex

Stacked organic light-emitting devices (OLEDs) based on a europium complex Eu(TTA)(3) (Tmphen) (TTA = thenoyltrifluoroacetone,Tmphen = 3,4,7,8-tetramethyl-1,10-phenanthroline) were fabricated. In this stacked OLEDs, Li:BCP/V2O5 was used the intermediate charge generation layer sandwiched between two identical emissive units consisting of TPD/CBP:DCJTB:Eu(TTA)(3)(Tmphen)/BCP. As expected, the brightness and electroluminescent (EL) current efficiency were approximately enhanced by double times that of conventional single-unit devices. The stacked OLEDs showed the maximum luminance up to 3000 cd/m(2) at a current density of 190 mA/cm(2) and a current efficiency of 14.5 cd/A at a current density of 0.08 mA/cm(2). At the brightness of 100 cd/m(2), the current efficiency reached 10 cd/A at a current density of 1.6 mA/cm2.

Highly efficient phosphorescent bis-cyclometalated iridium complexes based on quinoline ligands

The synthesis and electrochemical and photophysical study of a series of bis-cyclometalated iridium(III) complexes based on quinoline ligands have been carried out. These complexes are found to emit red-orange to deep red phosphorescence with high quantum yield and short lifetime. The red organic light-emitting diodes (OLEDs) with the external quantum efficiency up to 11.3% were demonstrated. Slow decay of efficiency with increasing current density was observed. These indicate that quinoline-based iridium complexes are promising candidates for efficient red emitters.