Organometallic complexes as hole-transporting materials in organic light-emitting diodes

The use of metal complexes fac-tris(1-phenylpyrazolato-N,C(2)('))cobalt(III) [fac-Co(ppz)(3)], fac-tris(2-phenylpyridinato-N,C(2)(') cobalt(III) [fac-Co(ppy)(3)], and [tris[2-((pyrrole-2-ylmethylidene)amino)ethyl]amine]gallium(III) [Ga(pma)] as materials for hole-transporting layers (HTL) in organic light-emitting diodes (OLEDs) is reported. Co(ppz)(3) and Co(ppy)(3) were prepared by following literature procedures and isolated as mixtures of facial (fac) and meridional (mer) isomers. The more stable fac isomers were separated from the unstable mer forms via column chromatography and thermal gradient sublimation. Crystals of fac-Co(ppz)(3) are monoclinic, space group P2(1)/c, with a = 13.6121(12) A, b = 15.5600(12) A, c = 22.9603(17) A, beta = 100.5 degrees, V = 4781.3(7) A(3), and Z = 8. [Tris[2-((pyrrol-2-ylmethylidene)amino)ethyl]amine]gallium [Ga(pma)] was prepared by the reaction of gallium(III) nitrate with the pmaH(3) ligand precursor in methanol. Ga(pma) crystallizes in the cubic space group I3d with cell parameters a = 20.2377(4) A, b = 20.2377(4) A, c = 20.2377(4) A, beta = 90.0 degrees, V = 8288.6(3) A(3), and Z = 16. These cobalt and gallium complexes are pale colored to colorless solids, with optical energy gaps ranging 2.6-3.36 eV. A two-layer HTL/ETL (ETL = electron-transporting layer) device structure using fac-Co(ppz)(3) and fac-Co(ppy)(3) as the HTL does not give efficient electroluminescence. However, the introduction of a thin layer of a hole-transporting material (N,N'-bis(1-naphthyl)-N,N'-diphenylbenzidine, NPD) as an energy "stair-step" and electron/exciton-blocker dramatically improves the device performance. Both fac-Co(ppz)(3) and fac-Co(ppy)(3) devices give external quantum efficiencies higher than 1.0%, with brightness 5000 and 7000 Cd/m(2) at 10 V, respectively. Ga(pma) also functions as an efficient interface layer, giving device performances very similar to those of analogous devices using NPD as the interface layer. Stability tests have been carried out for Co(ppz)(3)/NPD/Alq(3) and Co(ppy)(3)/NPD/Alq(3) devices. While fac-Co(ppy)(3) gave stable OLEDs, the fac-Co(ppz)(3)-based devices had very short lifetimes. On the basis of the experimental results of chemical oxidation of fac-Co(ppz)(3), the major cause for the fast decay of the fac-Co(ppz)(3) device is proposed to be the decomposition of fac-Co(ppz)(3)(+) in the HTL layer during the device operation.     

Homology classes that can be represented by embedded spheres in rational surfaces

The problem of embedding spheres in rational surfaces CP~2#nCP~2 is studied.For homology classes u=(b_1+k, b_2,…, b_n) with positive self-intersection numbers, anecessary and sufficient condition to detect its representability is given when k≤5.     

More About 4-Isosceles Planar Sets

A finite planar set is k-isosceles for k 3 if every k-point subset of the set contains a point equidistant from the other two. In [1] Fishburn obtains several important results about isosceles planar sets and poses a series of conjectures and open questions. We disprove Conjecture 1 in [1] and provide another 34 nonsimilar 4-isosceles 8-point planar sets which answer one of the open questions in [1] negatively.     

Global simulation for laser-driven MeV electrons in fast ignition

A comprehensive examination of the interaction of a picosecond-long ignition pulse on high-density (40 times critical density) pellets using a two-dimensional particle-in-cell model is described. The global geometry consists of a 50 mum diameter pellet surrounded by a corona which is isolated by a vacuum region from the boundary. For cone-attached targets, as much as 67% of the incident laser energy is absorbed with 12% sent forward as fast electrons in a 23 degrees cone. The current filaments are driven by the Weibel instability of the forward-going fast electron flux and its return current with the ions playing an important role of neutralizing the space charge. No global current filament coalescence has been observed. The electron distribution function obeys a power law, which begins at E approximately 0.2 MeV and falls off as E-(2-3).     

Optimal switching from recording to fixing for high diffraction from a LiNbO3:Ce:Cu photorefractive nonvolatile hologram

An oscillatory characteristic of diffraction is observed as a result of strong beam coupling in a weakly oxidized LiNbO3:Ce:Cu crystal during the recording step in the production of nonvolatile photorefractive holograms. On this basis the optimal switching time from the recording step to the fixing step for high diffraction of a fixed hologram is studied. It is shown that switching after the first diffraction maximum leads theoretically to fixed diffraction of as much as 100% with a suitable switching time. Both an experimental demonstration and a theoretical simulation are presented.     

Solid state and solution 43Ca NMR of calcium peroxides involved in the disproportionation of hydrogen peroxide by calcium hydroxide

In order to get some insight into the mechanism of the disproportionation of hydrogen peroxide catalyzed by calcium hydroxide, 43Ca NMR spectra of enriched samples of calcium peroxides and of their precursors have been studied in both solution and solid state. This study demonstrates that no well-defined peroxidized calcium species are formed in solution, showing that the catalytic role of calcium is likely restricted to the solid state. Most of the calcium compounds that could be involved in the catalytic process have been investigated with solid state NMR. The shift and quadrupolar parameters of Ca(OH)2, CaO2.8H2O and CaO2.2H2O2 are reported for the first time. These parameters are different enough to allow the quantitative analysis of a complex mixture of these compounds by NMR.     

Functionalization of polyoxometalates: from Lindqvist to Keggin derivatives. 1. synthesis, solution studies, and spectroscopic and ESI mass spectrometry characterization of the rhenium phenylimido tungstophosphate [PW11O39(ReNC6H5)]4-

Reaction of [Bu(4)N](4)[H(3)PW(11)O(39)] with [Re(NPh)Cl(3)(PPh(3))(2)], in acetonitrile and in the presence of NEt(3), provided the first Keggin-type organoimido derivative [Bu(4)N](4)[PW(11)O(39)(ReNPh)] (Ph = C(6)H(5)) (1). The functionalization was clearly demonstrated by various techniques including (1)H and (14)N NMR, electrochemistry, and ESI mass spectrometry. Conditions for the formation of 1 are also discussed.     

Preparation and characterization of a poled nanocrystal and polymer composite PbTiO3/PEKc film for electro-optic applications

Composite thin films of PbTiO₃ nanocrystals and high-transparency PEKc polymer for applications in electro-optical devices were prepared using the spin coating technique. The size of the PbTiO₃ nanocrystals was estimated to be 30–40 nm using a transmission electron microscope. The transmission technique, a simple method for measuring the electro-optic coefficients of poled composite polymer films was developed. The electro-optic coefficient γ₃₃ of poled PbTiO₃/PEKc composite polymer films was measured to be 18.34 pm  V^-1 at 633 nm under room temperature. The index at 633 nm and the dielectric constant at 100 kHz under room temperature were determined to be 1.65248 and 7.32, respectively. The figure of merit F₂=n⁷γ²/ε was estimated to be 1546, showing very good electro-optical properties. Received: 5 February 2002 / Accepted: 12 March 2002 / Published online: 19 July 2002 RID="*" ID="*"Corresponding author. Fax: +852/2788-7791, E-mail: eeytc@cityu.edu.hk     

Stereoselectivity of nitrile oxide cycloadditions to chiral allylic fluorides: experiment and theory

The cycloadditions of nitrile oxides with new and previously studied allylic fluorides were examined. The 1,3-dipolar cycloaddition reactions were also investigated theoretically with density functional theory (B3LYP) based transition-state modelling. The predictions provided reasonable agreement with experiment, indicating that both steric and electronic effects have important influences on the stereoselectivities of these reactions.     

Aptamer structures: a preview into regulatory pathways?

The crystal structure of a streptomycin binding RNA aptamer displays a novel bipartite fold able to clamp the antibiotic. In view of the recent findings that metabolites directly control mRNA translation, we might expect that similar structures exist in natural RNAs.