Nonconjugated Carbazoles: A Series of Novel Host Materials for Highly Efficient Blue Electrophosphorescent OLEDs

A series of carbazole derivatives was synthesized and their electrical and photophysical properties were investigated. It is shown that the triplet energy levels of these hosts are higher than that of the most popular blue phosphorescent material iridium(III) bis[(4,6-difluorophenyl)pyridinato-N,C-2'] picolinate (FIrpic) and the most extensively used phosphorescent host material 4,4'-N,N'-dicarbazole-biphenyl (CBP). These new host materials also showed good thermal stability and high glass transition temperatures (T-g) ranging from 78 to 115 degrees C as the linkage group between the carbazoles was altered. Photophysical measurements indicate that the energy transfer between these new hosts and FIrpic is more efficient than that between CBP and FIrpic. Devices incorporating these novel carbazole derivatives as the host material doped with FIrpic were fabricated with the configurations of ITO/NPB (40 nm)/host:FIrpic (30 nm)/BCP (15 nm)/AlQ (30 nm)/LiF (1 nm)/Al (150 nm). High efficiencies (up to 13.4 cd/A) have been obtained when 1,4-bis (4-(9H-carbazol-9-yl)phenyl)cyclohexane (CBPCH) and bis(4-(9H-carbazol-9-yl)phenyl) ether (CBPE) were used as the host, respectively.

3D 异金属Bi(III)-Pr(III)配位聚合物的合成、晶体结构和热稳定性

在水溶液中合成了双金属配位聚合物({[(NO3)(H2O)3Pr(μ4-Hedta)Bi-(NO3)2].2H2O}2)n,并通过元素分析、红外光谱和X射线单晶衍射等手段进行了表征.该配合物为单斜晶系,P2(1)/n空间群,a=1.26831(18)nm,b=0.82189(12)nm,c=2.3755(3)nm,β=105.055(2)°,R=0.0429,V=2.3913(6)nm3,Z=4.Bi(Ⅲ)-Pr(Ⅲ)间通过配阴离子Hedta3-中4个羧基的桥联作用构建配合物的3D结构.TG-DSC结果表明,该配合物热分解经历脱水、配体分解以及盐分解过程,残余物为Bi-Pr-O的三元复合氧化物.

Improved efficiency by doping blue iridium (III) complex in europium complex-based light-emitting diodes

We demonstrated high-efficiency red organic light-emitting diodes (OLEDs) employing a europium complex, Eu (III) tris( thenoyltrifluoroacetone) 3,4,7,8-tetramethyl-1,10-phenanthroline (Eu(TTA)(3)(Tmphen)), as an emitter and a blue electrophosphorescent complex, Iridium ( III) bis[4,6-di-fluorophenyl-pyridinato-N,C-2] picolinate (FIrpic), as an assistant dopant codoped into 4,4-N, N-dicarbazole-biphenyl (CBP) host as an emissive layer. A pure red electroluminescence (EL) only from Eu3+ ions at 612 nm with a full width at half maximum of 3 nm was observed and the EL efficiency was significantly enhanced. The maximum EL efficiency reached 7.9 cd A(-1) at 0.01 mA cm(-2) current density, which is enhanced by 2.8 times compared with electrophosphorescence-undoped devices. The large improvements are attributed to energy transfer assistance effects of FIrpic, indicating a promising method for obtaining efficient red OLEDs based on rare-earth complexes.

Pyrrolide-supported lanthanide alkyl complexes. Influence of ligands on molecular structure and catalytic activity toward isoprene polymerization

The N,N- bidentate ligands 2- {( N- 2,6- R) iminomethyl)} pyrrole ( HL1, R) dimethylphenyl; HL2, R) diisopropylphenyl) have been prepared. HL1 reacted readily with 1 equiv of lanthanide tris( alkyl)s, Ln(CH2SiMe3)(3)(THF)(2), affording lanthanide bis(alkyl) complexes L(1)Ln(CH2SiMe3)(2)(THF)(n) (1a, Ln= Lu, n = 2; 1b, Ln = Sc, n = 1) via alkane elimination. Reaction of the bulky ligand HL2 with 1 equiv of Ln(CH2SiMe3)(3)( THF)(2) gave the bis(pyrrolylaldiminato) lanthanide mono(alkyl) complexes L(2)(2)Ln- (CH2SiMe3)(THF) (2a, Ln) Lu; 2b, Ln = Sc), selectively. The N,N- bidentate ligand HL3, 2- dimethylaminomethylpyrrole, reacted with Ln( CH2SiMe3) 3( THF) 2, generating bimetallic bis( alkyl) complexes of central symmetry ( 3a, Ln = Y; 3b, Ln = Lu; 3c, Ln = Sc). Treatment of the N,N,N,N- tetradentate ligand H2L4, 2,2'-bis(2,2-dimethylpropyldiimino) methylpyrrole, with equimolar Lu(CH2SiMe3)(3)(THF)(2) afforded a C-2- symmetric binuclear complex ( 4). Complexes 3a, 3b, 3c, and 4 represent rare examples of THF- free binuclear lanthanide bis( alkyl) complexes supported by non- cyclopentadienyl ligands. All complexes have been tested as initiators for the polymerization of isoprene in the presence of AlEt3 and [ Ph3C][B(C6F5)(4)]. Complexes 1a, 1b, and 3a show activity, and 1b is the most active initiator, whereas 2a, 2b, 3b, 3c, and 4 are inert.

PH-Dependent syntheses and structures of two Copper(II)/Phenanthroline/p-Sulfonatocalix[4]arene supramolecular compounds with 1D water-filled channels

Two copper-organic framework supramolecular assemblies of p-sulfonatocalix[4]arene and 1,10-phenanthroline Cu-2[C12H8N2][C28H20S4O16][H2O](23.5) (1) and Cu-3[C12H8N2](3)[C28H19S4O16]Cl[H2O](17.6) (2) were obtained by pH-dependent synthesis at room temperature. Both structures show ID water-filled channels (rectangular shape in I and triangular in 2) with the solvent-accessible volume occupying 30.8% (1) and 24.2% (2) of the unit-cell volume, respectively. The calixarene molecules in both structures assume analogous cone shapes of C-2 nu symmetry instead of the conventional C-4 nu symmetry. Their connecting to different amounts of copper/phenanthroline cations leads to the formation of different structures.

Synthesis and characterization of white-light-emitting polyfluorenes containing orange phosphorescent moieties in the side chain

Two orange phosphorescent iridium complex monomers, 9-hexyl-9-(iridium (III)bis(2-(4'-fluorophenyl)-4-phenylquinoline-N, C-2')(tetradecanedionate-11,13))-2,7-dibromofluorene (Br-PIr) and 9-hexyl-9-(iridium(III)bis(2-(4'-fluorophenyl)-4-methylquinoline-N, C-2')(tetradecanedionate-11,13))-2,7-dibromofluorene (Br-MIr), were successfully synthesized. The Suzuki polycondensation of 2,7-bis(trimethylene boronate)-9,9-dioctylfluorene with 2,7-dibromo-9,9-dioetylfluorene and Br-Plr or Br-MIr afforded two series of copolymers, PIrPFs and MIrPFs, in good yields, in which the concentrations of the phosphorescent moieties were kept small (0.5-3 mol % feed ratio) to realize incomplete energy transfer. The photoluminescence (PL) of the copolymers showed blue- and orange-emission peaks. A white-light-emitting diode with a configuration of indium tin oxide/poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate)/PIr05PF (0.5 mol % feed ratio of Br-PIr)/Ca/Al exhibited a luminous efficiency of 4.49 cd/A and a power efficiency of 2.35 lm/W at 6.0 V with Commission Internationale de L'Eclairage (CIE) coordinates of (0.46, 0.33). The CIE coordinates were improved to (0.34, 0.33) when copolymer MIr10PF (1.0 mol % feed ratio of Br-MIr) was employed as the white-emissive layer. The strong orange emission in the electroluminescence spectra in comparison with PL for these kinds of polymers was attributed to the additional contribution of charge trapping in the phosphorescent dopants.

New titanium complexes with two beta-enaminoketonato chelate ligands: Syntheses, structures, and olefin polymerization activities

New titanium complexes with two nonsymmetric bidentate beta-enaminoketonato (N,O) ligands (4a-e), [(Ph)NC(R-2)C(H)C(R-1)O](2)TiCl2, have been synthesized. X-ray crystal structure reveals that complex 4a has a C-2-symmetric conformation with a distorted octahedral geometry around the titanium center. With modified methylaluminoxane (MMAO) as a cocatalyst, complexes 4a-e are active catalysts for ethylene polymerization at room temperature, producing high molecular weight polyethylenes bearing linear structures. The 4a,b/MMAO catalyst systems exhibit the characteristics of a quasi-living polymerization of ethylene, producing polyethylenes with narrow molecular weight distributions. Moreover, the 4a-d/MMAO catalyst systems are also capable of promoting the quasi-living copolymerization of ethylene with norbornene at room temperature, yielding high molecular weight alternating copolymers with narrow molecular weight distributions. The quasi-living nature of the catalysts allows the synthesis of new A-B polyethylene-block-poly(ethylene-conorbornene) diblock copolymer.

含苯并咪唑基配体的稀土配合物的合成、结构及量子化学研究

合成了未见文献报道的N,N,N',N'-四[(2-苯并咪唑)甲基]乙二胺的丁基取代衍生物(BuEDTB)与稀土硝酸盐的配合物[M(BuEDTB)(NO3)2]·NO3·4H2O[M=La(1),Eu(2),Tb(3)],并用X射线衍射法测定了1的结构.晶体属三方晶系,空间群P3221,晶胞参数a=1.41353(9)nm,c=2.6264(4)nm;V=4.5447(9)nm3,Dc=1.189g/cm3,Z=3,F(000)=1686,μ=0.758 mm-1,R=0.0562,wR=0.1488.乙二胺上两个N原子及四个苯并咪唑各有一个N原子参与配位,两个硝酸根以双齿形式与稀土离子配位,第三个硝酸根不与金属离子配位.用ab initio HF方法研究了BuEDTB的电子结构.

聚电解质溶液浓度区域的划分

按照DeGennes[1] 提出的标度概念 ,柔性高分子溶液可以划分为稀溶液 ,亚浓溶液和浓溶液 3个区域 ,它们之间分别以接触浓度c 和交叠浓度c 为分界线 .钱人元等[2 ] 根据聚苯乙烯溶液激基荧光强度浓度依赖性的实验结果 ,提出稀溶液区还应细分为极稀溶液和稀溶液两个区域 ,它的分界浓度称为动态接触浓度cs.中性高分子溶液存在这一分界浓度 ,已经得到体积排除色谱[3 ] 、高分子溶液的物理凝胶化[4] 、以及动态光散射[5] 等研究结果的证实 .本文作者之一 (程 )从中性高分子在溶液中由于范德华分子间吸引力的存在容易自缔合而形成团族的概念出发 ,导出了溶液粘度与cs 之间的理论关系[6,7] .聚电解质由于在溶液中可以离解为聚离子和对离子的特性 ,关于它的溶液浓度区域的划分问题 ,已经引发了一些理论的[8～ 11] 和许多实验的研究 ,其中包括光散射[12～ 14 ] 、小角X射线散射[15] 、小角中子散射[16] 、准弹性中子散射[17] 、溶液电导[18] 和溶液粘度[19]等 .这些研究中的绝大多数 ,仍然将溶液划分为稀溶液 ,亚浓溶液和浓溶液 3个区域.

Radical co-polymerization of diiminedibromidenickel(II)-functionalized olefin with styrene: synthesis of polymer-incorporated nickel(II) alpha-diimine catalysts for ethylene polymerization

alpha-Diimine nickel catalyst hearing two allyl groups [ArN=C](2)C10H6NiBr2 (Ar = 4-allyl-2,6-(i-Pr)(2)C6H2)] (Cat-I) has been synthesized and characterized. The corresponding polymer-incorporated nickel catalysts PC and the SiO2-supported shell-core structure catalyst SC-1 were obtained by the co-polymerization of the olefin groups of Cat-1 with styrene in the presence of a radical initiator. Radical co-polymerizations with styrene in Solution were investigated in detail, and the compositions and molecular weight of the copolymers were determined. All three types of catalysts (Cat-1, PC and SC-1) have been investigated for ethylene polymerization. These catalysts were found to exhibit high activity in the presence of modified methylaluminoxane (MMAO) as a co-catalyst. Among them, the polymer-incorporated PC and SiO2 shell-core catalyst SC-1 displayed very high activity (similar to2.62 and similar to1.11 kg (mmol Ni)(-1) h(-1), respectively) with product molecular weights (M,) in the range 26 x 10(4) to 47 x 10(4) under 0.1 MPa ethylene pressure. The particle morphology of polyethylene produced by the shell-core structure catalyst SC-1 was improved.

Micron-granula polyolefin with self-immobilized nickel and iron diimine catalysts bearing one or two allyl groups

Self-immobilized nickel and iron diimine catalysts bearing one or two allyl groups of [ArN=C](2)(C10H6)NiBr2 [Ar = 4-allyl-2,6-(i-Pr)(2)C6H2] (1), [ArN=C(Me)[Ar'N=C(Me)]C5H3NFeCl2 [Ar = Ar' = 4-allyl-2,6-(i-Pr)(2)C6H3, Ar = 2,6-(i-Pr)(2)C6H3, and Ar' = 4-allyl-2,6-(i-Pr)(2)C6H3] were synthesized and characterized. All three catalysts were investigated for olefin polymerization. As a result, these catalysts not only showed high activities as the catalyst free from the allyl group, such as [ArN=C](2)C10H6,NiBr2 (Ar = 2,6-(i-Pr)(2)C6H2)], but also greatly improved the morphology of polymer particles to afford micron-granula polyolefin. The self-immobilization of catalysts, the formation mechanism of microspherical. polymer, and the influence on the size of the particles are discussed. The molecular structure of self-immobilized nickel catalyst 1 was also characterized by crystallographic analysis.

Preparation and characterization of a novel solid solution of aluminum in tungsten carbide by mechanically activated high-temperature reaction

In this work, a novel substitutional solid solution (W0.8Al0.2)C was synthesized by mechanically activated high-temperature reaction. X-ray diffraction was used for phase identification during the whole reaction process. Environment scanning electronic microscopy-field emission gun and energy dispersive x-ray were used to investigate the microstructure and the quantitative material composition of the specimen. (W(0.8)A(10.2))C was found to crystallize in the WC-type, and the cell parameters were a = 2.907(1) angstrom and c = 2.837(1) angstrom. The hardness of (W0.8Al0.2)C was tested to be 19.3 +/- 1 GPa, and the density was 13.19 +/- 0.05 g cm(-3).

New neutral nickel(II) complexes bearing pyrrole-imine chelate ligands: synthesis, structure and norbornene polymerization behavior

New neutral nickel(II) complexes bearing nonsymmetric bidentate pyrrole-imine chelate ligands (4a-d), [2-(ArNCH)C4H3N]Ni(PPh3)Ph [Ar=2,6-diisopropylphenyl (a), 2-methyl-6-isopropylphenyl (b), 2,6-diethylphenyl (c), 2-tert-butylphenyl (d)], have been prepared in good yields from the sodium salts of the corresponding ligands and trans-Ni(PPh3)(2)(Ph)Cl, and the structure of complex 4a has been confirmed by X-ray crystallographic analysis. These neutral Ni(II) complexes were investigated as catalysts for the vinylic polymerization of norbornene. Using modified methylaluminoxane (MMAO) as a cocatalyst, these complexes display very high activities and produce great mass polymers. Catalyst activity of up to 4.2 x 10(7) g (mol Ni h)(-1) and the viscosity-average molecular weight of polymer of up to 9.2 x 10(5) g mol(-1) were observed. Catalyst activity, polymer yield, and polymer molecular weight can be controlled over a wide range by the variation of reaction parameters such as Al-Ni ratio, norbornene-catalyst ratio, monomer concentration, polymerization reaction temperature and time.

Synthesis, electrocatalytic properties and crystal structure of a new organic-inorganic hybrid constructed from dodecamolybdophosphoric acid and benzotriazole

A new compound, (C6H6N3)(7)((PMo12O40)-O-m)(PMo(v)Mo(11)(m)O40) (.) 2CH(3)CH(2)OH (.) 5H(2)O, was synthesized and characterized by means of elemental analyses, IR spectroscopy, H-1 NMR spectroscopy and single crystal X-ray diffraction. This is the first example of benzotriazole-polyoxometalates species. The compound crystallized in a triclinic space group P (1) over bar with a = 1. 8378 (4) nm. b = 1. 9078 (4) nm. c = 2.1037 (4) nm. alpha = 63.41 (3)degrees. beta = 64.31 (3)degrees. gamma = 68.38 (3)degrees. V = 5.803 (2) nm(3). Z = 2. R-1 = 0.0486, wR(2) = 0.1357. The X-ray crystallographic study showed that the crystal structure was constructed by electrostatic interactions and hydrogen bonds between dodecamolybdophosphorate anions and protonated benzotriazole cations. The electrochemical behavior and the reduction of nitrite and hydrogen peroxide clectrocatalyzed by the title compound were studied.

Synthesis and characterization of novel lanthanocene complexes with dichalcogenolate o-carboranyl ligands

Reactions of [ Cp(2)Ln(mu-Cl)](2) (Cp = eta(5)-C5H5, Ln = Nd, Yb, Dy, Gd, Er) with an equivalent of [ (THF)(3)LiE2C2B10H10Li. (TT-IF) (THF)](2) (E = S, Se) in THF afforded the dinuclear sandwich complexes of formula[Cp(2)LnE(2)C(2)B(10)H(10)](2)[Li(THF)(4)](2) [E = S, Ln = Nd (1a), Yb (2a), Dy (3a), Gd (4a), Er (5a); E = Se, Ln = Nd (1b), Yb (2b), Dy (3b), Gd (4b), Er (5b)]. The molecular structures of complexes la, 2a and 2b were determined by the single crystal X-ray structure analyses. Two lanthanide atoms are connected by a pair chalcogen (eta(1), eta(2)-E2C2B10H10) bridging ligands and the central Ln(2)E(2) four membered ring is not planar.