Structure of an unexpected trimer from the reaction of ageratochromene II with aluminum chloride

A new trimer from the reaction of ageratochromene [1] (6,7-dimethoxy-2,2-dimethyl-1-benzopyran) with anhydrous aluminum chloride was shown to be 3,4-dihydro-6,7-dimethoxy-2,2-dimethyl-3-(6',7'-dimethoxy-2',2'-di-methyl-2H-1-benzopyran-4'-yl)-4-(3" 4"-dihydro-6", 7"-dimethoxy-2",2"-dimethyl-2H-1-benzopyran-3"-yl)-2H-1-benzopyran. Its structure was confirmed by NMR (H-1, C-13, DEPT-135. COSY, HMBC, HSQC, TOCSY and NOESY), IR, mass spectra and elemental analysis. Copyright (C) 2002 John Wiley Sons, Ltd.

Cesium hydroxide doped tris-(8-hydroxyquinoline) aluminum as an effective electron injection layer in inverted bottom-emission organic light emitting diodes

We demonstrate highly efficient inverted bottom-emission organic light-emitting diodes (IBOLEDs) by using cesium hydroxide (CsOH) doped tris-(8-hydroxyquinoline) aluminum (Alq(3)) as the electron injection layer on indium tin oxide cathode, which could significantly enhance the electron injection, resulting in a large increase in luminance and efficiency. The maximum luminance, current efficiency, and power efficiency reach 21 000 cd/cm(2), 6.5 cd/A, and 3.5 lm/W, respectively, which are 40%-50% higher in efficiency than that of IBOLEDs with cesium carbonate (Cs2CO3) doped Alq(3) as the electron injection layer, where the efficiencies are only 4.5 cd/A and 2.2 lm/W.

Origin of negative differential resistance and memory characteristics in organic devices based on tris(8-hydroxyquinoline) aluminum

Negative differential resistance (NDR) and memory phenomenon have been realized in current-voltage (I-V) characteristics of indium tin oxide/tris(8-hydroxyquinoline) aluminum/aluminum devices. The I-V curves have been divided into three operational regions that are associated with different working regimes of the devices: (i) bistable region, (ii) NDR region, and (iii) monotonic region. The bistable region disappeared after a couple of voltage sweeps from zero to a positive voltage. The bistable nature can be reinstated by applying a suitable negative voltage.

Enolic Schiff base aluminum complexes and their catalytic stereoselective polymerization of racemic lactide

A series of enolic Schiff base aluminum(III) complexes LAIR (where L = NNOO-tetradentate enolic Schiff base ligand) containing ligands that differ in their steric and electronic properties were synthesized. Their single crystals showed that these complexes are five -coordinated around the aluminum center. Their coordination geometries are between square pyramidal and trigonal bipyramidal. Their catalytic properties in the solution polymerization of racemic lactide (rac-LA) were examined. The modifications in the auxiliary ligand exhibited a dramatic influence on the catalytic performance.

Copolymerization of carbon dioxide and cyclohexene oxide catalyzed by aluminum porphyrin-quaternary ammonium salt in the presence of bulky lewis acid

Chloro( 5,10,15,20-tetraphenyl-porphyrinato)-aluminum/tetraethylammonium bromide ( Et4NBr) in combination with bulky Lewis acid was used for the copolymerization of CO2 and cyclohexene oxide ( CHO). Bulky Lewis acid having substituents at the ortho positions of the phenolate ligands, like methylaluminum bis(2,6-di-tert-butyl-4-methylphenolate), significantly shortened the induction period and raised the catalytic activity, the corresponding turnover frequency reached 44.9 h(-1) in 9 h, which was 23.8% higher than that from ( TPP)AlCl/Et4NBr binary catalyst. The resulting polycarbonate has carbonate linkage over 93% with number average molecular weight of ( 4.5-6.5) x 10(3) and polydispersity index below 1.10.

Polymerization of Lactide Using Achiral Bis(pyrrolidene) Schiff Base Aluminum Complexes

A series of aluminum ethyls and isopropoxides based on a bis(pyrrolidene) Schiff base ligand framework has been prepared and characterized. NMR studies of the dissolved complexes indicate that they adopt a symmetric structure with a monomeric, five-coordinated aluminum center core. The aluminum ethyls used as catalysts in the presence of 2-propanol as initiator and the aluminum isopropoxides were applied for lactide polymerization in toluene to test their activities and stereoselectivities. All polymerizations are living, as evidenced by the narrow polydispersities and the good fit between calculated and found number-average molecular weights of the isolated polymers. All of these aluminum complexes polymerized (S,S)-lactide to highly isotactic PLA without epimerization of the monomer, furnished isotactic-biased polymer from rac-lactide, and gave atactic polymer from meso-lactide.

Origin of improvement in device performance via the modification role of cesium hydroxide doped tris(8-hydroxyquinoline) aluminum interfacial layer on ITO cathode in inverted bottom-emission organic light-emitting diodes

It has been found that cesium hydroxide (CsOH) doped tris(8-hydroxyquinoline) aluminum (Alq(3)) as an interfacial modification layer on indium-tin-oxide (ITO) is an effective cathode structure in inverted bottom-emission organic light-emitting diodes (IBOLEDs). The efficiency and high temperature stability of IBOLEDs with CsOH:Alq(3) interfacial layer are greatly improved with respect to the IBOLEDs with the case of Cs2CO3:Alq(3). Herein, we have studied the origin of the improvement in efficiency and high temperature stability via the modification role of CsOH:Alq(3) interfacial layer on ITO cathode in IBOLEDs by various characterization methods, including atomic force microscopy (AFM), ultraviolet photoemission spectroscopy (UPS), X-ray photoemission spectroscopy (XPS) and capacitance versus voltage (C-V). The results clearly demonstrate that the CsOH:Alq(3) interfacial modification layer on ITO cathode not only enhances the stability of the cathode interface and electron-transporting layer above it. which are in favor of the improvement in device stability, but also reduces the electron injection barrier and increases the carrier density for current conduction, leading to higher efficiency.

Efficient multilayer white polymer light-emitting diodes with aluminum cathodes

Efficient multilayer white polymer light-emitting diodes (WPLEDs) with aluminum cathodes are fabricated. The multilayer structure is composed of a water soluble hole-injection layer, a toluene-soluble emissive layer, and an alcohol-soluble emissive layer. The polarity difference of the solvents used for spin coating these polymers allows for realization of the multilayer polymer structure. The recombination zone confined at the interface of the two emissive polymers avoids exciton quenching by electrodes, and white emission is realized by harvesting photons emitted from the two emissive polymers. A maximum luminous efficiency of 16.9 cd/A and a power efficiency of 11.1 lm/W are achieved for this WPLED.

Improvement of amplified spontaneous emission performance by doping tris(8-hydroxyquinoline) aluminum (Alq3) in dye-doped polymer thin films

A well-known red fluorescent dye 4-(dicy-anomethylene)-2-t-butyl-6(1,1,7,7-tetramethyljulolidyl-9-enyl)4H-pyran (DCJTB) was codoped with an electron transport organic molecule tris(8-hydroxyquinohne) aluminum (Alq3) in a host matrix of polystyrene (PS), and the amplified spontaneous emission (ASE) was studied by optically pumping. It was found that the ASE performance was significantly improved by the introduction of Alq3. The Alq3:DCJTB:PS blending thin films showed a low threshold (2.4 mu J/pulse) and a high net gain coefficient (109.95 cm(-1)) compared with the pure DCJTB:PS system (threshold of 15.2 mu J/pulse and gain of 35.94 cm(-1)). The improvement of the ASE performance was considered to be attributable to the effective Foster energy transfer from Alq(3) to DCJTB. Our results demonstrate that the Alq(3):DCJTB could be a promising candidate as gain medium for red organic diode lasers.

High gain in hybrid transistors with vanadium oxide/tris(8-hydroxyquinoline) aluminum emitter

We report the electrical characterization of hybrid permeable-base transistors with tris(8-hydroxyquinoline) aluminum as emitter layer. These transistors were constructed presenting an Al/n-Si/Au/Alq(3)/V2O5/Al structure. We investigate the influence of the V2O5 layer thickness and demonstrate that these devices present high common-base and common-emitter current gain, and can be operated at very low driving voltages, lower than 1 V, in both, common-base and common-emitter modes.

Polymerization of rac-lactide using schiff base aluminum catalysts: Structure, activity, and stereoselectivity

A series of aluminum ethyls and isopropoxides based upon N,N,O,O-tetradentate Schiff base ligand framework have been prepared. X-ray diffraction analysis and H-1 NMR confirmed that these Schiff base aluminum ethyls and isopropoxides were all monomeric species with a five-coordinated central aluminum in their solid structures. Compared to the aluminum ethyls which all retain their monomeric structure in the solution, the dinucleating phenomenons of aluminum isopropoxides with less steric hindered substituents in the solution have also been observed. The activities and stereoselectivities of these complexes toward the ring-opening polymerization of rac-lactide have been investigated. Polymerization experiments indicated that (SB-2d)(AlOPr)-Pr-i [(SB-2d) = 2,2-dimethyl-1,3-propylenebis(3,5-di-tert-butylsalicylideneiminato)] exhibited the highest stereoselectivity and (SB-3b)(AlOPr)-Pr-i [(SB-3b) = 2,2-dimethyl-1,3-propylenebis(3,5-dichlorinesalicylideneiminato)] possessed the highest activity among these aluminum isopropoxides. The substituents and the mode of the bridging part between the two nitrogen atoms both exerted significant influences upon the progress of the polymerizations, influencing either the tacticity of isolated polymers or the rate of polymerization.

Enolic Schiff-base aluminum complexes and their application in lactide polymerization

A series of NNOO-tetradentate enolic Schiff-base ligands were prepared where ligand L-1 = bis(benzoylacetone)propane-1,2-diimine, L-2 = bis(acetylacetone)-propane-1,2-diimine, L-3 = bis-(acetylacetone)cyclohexane-1,2-diimine. Their further reaction with aluminum tris(ethyl) formed complexes LAlEt (1a, 2a and 3a). The solid structure of complexes la, 2a and 3a confirmed by X-ray single crystal analysis manifested that these complexes were all monomeric and five-coordinated with an aluminum atom in the center. The configurations of these complexes varied from trigonal bipyramidal geometry (tbp) to square pyramidal geometry (sqp) due to their different auxiliary ligand architectures. H-1 NMR spectra indicated that all these complexes retained their configuration in solution states. Their catalytic properties to polymerize racemic-lacticle (rac-LA) in the presence of 2-propanol were also studied. The diimine bridging parts as well as the diketone segment substituents had very close relationship with their performance upon the polymerization process. All these complexes gave moderately isotactic polylactides with controlled molecular weight and very narrow molecular weight distributions.

Stereoselective polymerization of rac-lactide with a bulky aluminum/Schiff base complex

An aluminum/Schiff base complex {[2,2-dimethyl-1,3-propylenebis(3,5-di-tert-butylsalicylideneiminato)](isopropanolato)aluminum(III) (2)} based on a bulky ligand and aluminum isopropoxide was prepared and employed for the stereoselective ring-opening polymerization (ROP) of rac-lactide (rac-LA). The initiator was characterized with nuclear magnetic resonance (NMR), crystal structure measurements, and elemental analysis. It contained a five-coordinate aluminum atom that was trigonal bipyramidal in the solid state according to the crystal structure measurements. The two conformational stereoisomers of 2 exchanged quickly on the NMR scale. Compound 2 polymerized rac-LA into a crystalline polymer that was characterized with H-1 NMR, wide-angle X-ray diffraction, electrospray ionization mass spectrometry, and gel permeation chromatography. The kinetics of the polymerization were first-order in both the monomer and initiator, and there was a linear relationship between the rac-LA conversion and the number-average molecular weight of poly(rac-LA) with a narrow molecular distribution (1.04-1.08). These features showed that the polymerization was well controlled. The high melting temperature (196-201 degreesC) and isotacticity of poly(rac-LA) indicated that complex 2 was a highly stereoselective initiator for the ROP of rac-LA.

Efficient blue electroluminescence from neutral alcohol-soluble polyfluorenes with aluminum cathode

Efficient blue polymer light-emitting diodes (PLEDs) have been fabricated with a neutral alcohol-soluble polyfluorene, i.e., poly(9,9-bis(6(')-diethoxylphosphorylhexyl)fluorene) (PF-EP), as the emitting layer, high work-function Al as the cathode, and poly(vinyl carbazole) as the hole-transporting layer. The PLEDs display a maximum luminous efficiency of 4.0 cd/A and the luminous efficiency > 2.4 cd/A in a wide range of current densities. It is found that the promising performance of the devices is attributed to the fact that the PF-EP is not only an efficient blue light-emitting polymer, but it also can facilitate efficient electron injection at the Al/PF-EP interface.