2,2,9,9‐Tetramethylcyclonona‐3,5,7‐trienylidene vs. its heterocyclic analogues: A quest for stable carbenes at DFT

Replacement of α‐methylenes with BH, AlH, CMe₂, SiH₂, NH, NMe, N^tButyl, NPh, PH, O, and S in non‐planar cyclonona‐3,5,7‐trienylidene (CH₂) alters its status from an unstable transition state to rather stable minima, at B3LYP/6‐311++G**//B3LYP/6‐31 + G* levels of theory. All species appear with singlet closed shell (S_cs) global minima, except for SiH₂ and CH₂ which exhibit triplet electronic ground states. The order of stability based on singlet–triplet energy gap (ΔE_s–t / kcalmol^?1) is: CMe₂ (45.8) > NH (35.8) > NMe (32.3) > O (31.5) > N^tButyl (27.7) ≥ NPh (27.5) ≥ BH (27.4) > S (21.9) > PH (17.0) > CH₂ (?4.4) > SiH₂ (?12.5). In contrast to many reports on N‐heterocyclic carbenes, here alkyl groups appear to exert a higher stabilizing effect than heteroatoms, making CMe₂ the most stable. In addition bulky NMe, N^tButyl, and NPh appear more nucleophilic than their synthesized imidazol‐2‐ylidene congeners. Excluding SiH₂, isodesmic reactions reveal that all substituents stabilize singlet state considerably more than the corresponding triplet. Finally, this work is hoped to pave the path for future matrix isolations and IR studies of these rather stable cyclic non‐planar carbenes. Copyright © 2013 John Wiley & Sons, Ltd.     

Direct observation of the potential distribution within organic light emitting diodes under operation

We show the first direct measurement of the potential distribution within organic light emitting diodes (OLEDs) under operation and hereby confirm existing hypotheses about charge transport and accumulation in the layer stack. Using a focused ion beam to mill holes in the diodes we gain access to the cross section of the devices and explore the spatially resolved potential distribution in situ by scanning Kelvin probe microscopy under different bias conditions. In bilayer OLEDs consisting of tris(hydroxyquinolinato) aluminum (Alq₃)/N, N ′‐bis(naphthalene‐1‐yl)‐N,N ′‐bis(phenyl) benzidine (NPB) the potential exclusively drops across the Alq₃ layer for applied bias between onset voltage and a given transition voltage. These findings are consistent with previously performed capacitance–voltage measurements. The behavior can be attributed to charge accumulation at the interface between the different organic materials. Furthermore, we show the potential distribution of devices with different cathode structures and degraded devices to identify the cathode interface as main culprit for decreased performance. (© 2015 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Electronic properties of phenanthrimidazoles as hole transport materials in organic light emitting devices and in photoelectron transfer to ZnO nanoparticles

Phenanthrimidazoles as hole transport materials have been synthesized, characterized, and applied as nondoping emitters in organic light emitting devices. The synthesized molecules possess high fluorescent quantum yield and thermal properties and display film forming abilities. The highest occupied molecular orbital (HOMO) energies of these materials are shallower than the reported tris(8‐hydroxyquinoline)aluminum (Alq₃), which enables the hole transport ability of these phenanthrimidazoles. Taking advantage of the thermal stability and hole transporting ability, these compounds can be used as a functional layer between NPB [4,4‐bis(N‐(1‐naphthyl)‐N‐phenylamino)biphenyl] and Alq₃ layers and show that these phenanthrimidazoles can be alternatively used as novel hole transport materials and to improve the device performances. Geometrical, optical, electrical, and electroluminescent properties of these molecules have been probed. Further, natural bond orbital, nonlinear optical materials (NLO), molecular electrostatic potential, and HOMO–lowest unoccupied molecular orbital (LMO) energy analysis have been made by density functional theory (DFT) method to support the experimental results. Hyperpolarizability analysis reveals that the synthesized phenanthrimidazoles possess NLO behavior. The chemical potential, hardness, and electrophilicity index of phenanthrimidazoles have also been computed by DFT method. Photoinduced electron transfer explains the enhancement of fluorescence by nanoparticulate ZnO, and the apparent binding constant has been obtained. Adsorption of the fluorophore on ZnO nanoparticle lowers the HOMO and LUMO energy levels of the fluorophore. The strong adsorption of the phenanthrimidazoles on the surface of ZnO nanocrystals is likely due to the chemical affinity of the nitrogen atom of the organic molecule to Zn(II) on the surface of nanocrystal. Copyright © 2013 John Wiley & Sons, Ltd.     

Simple near‐infrared photodetector based on charge transfer complexes formed in molybdenum oxide doped N,N′‐di(naphthalene‐1‐yl)‐N,N′‐diphenyl‐benzidine

We have demonstrated a simple near‐infrared (NIR) photodetector (PD) based on charge transfer complex (CTC) formed in molybdenum trioxide (MoO₃) doped N,N′‐di(naphthalene‐1‐yl)‐N,N′‐diphenyl‐benzidine (NPB), which shows a photocurrent of about 0.35 A/cm² at –3 V under 980 nm illumination. The existence of CTC formation promotes photocurrent generation which is investigated by comparison with MoO₃ doped 2‐methyl‐9,10‐di(2‐naphthyl)anthracene (MADN) film which has no CTC absorption. It can be evolved that this kind of simple‐structure photodetector has potential application in the near‐infrared (NIR) detection area. It is shown in this Letter that although both MoO₃ and NPB have larger energy gaps of about 3 eV and weak absorption in the NIR region, the charge transfer complexes formed by mixing the two materials show an extra absorption band and good photoelectric response in the NIR region.

     

Electroluminescence enhancement in ultraviolet organic light‐emitting diode with graded hole‐injection and ‐transporting structure

Electroluminescent intensity and external quantum efficiency (EQE) in ultraviolet organic light‐emitting diodes (UV OLEDs) have been remarkably enhanced by using a graded hole‐injection and ‐transporting (HIT) structure of MoO₃/N,N ′‐bis(naphthalen‐1‐yl)‐N,N ′‐bis(phenyl)‐benzidine/MoO₃/4,4′‐bis(carbazol‐9‐yl)biphenyl (CBP). The graded‐HIT based UV OLED shows superior short‐wavelength emis‐ sion with spectral peak of ～410 nm, maximum electroluminescent intensity of 2.2 mW/cm² at 215 mA/cm² and an EQE of 0.72% at 5.5 mA/cm². Impedance spectroscopy is employed to clarify the enhanced hole‐injection and ‐transporting capacity of the graded‐HIT structure. Our results provide a simple and effective approach for constructing efficient UV OLEDs. (© 2015 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Theoretical investigations of pyridine derivatives as potential high energy density materials

Density function theory has been employed to study pyridine derivatives at the B3LYP/6‐31 G(d,p) and B3P86/6‐31 G(d,p) levels. The crystal structures were obtained by molecular mechanics methods. The heats of formation (HOFs) were predicted based on the isodesmic reactions. Detonation performance was evaluated by using the Kamlet–Jacobs equations based on the calculated densities and HOFs. The thermal stability of the title compounds was investigated by the bond dissociation energies and the energy gaps (ΔE_LUMO?HOMO) predicted. It is found that there are good linear relationships between detonation velocity, detonation pressure, and the number of nitro group. The simulation results reveal that molecule G performs similar to the famous explosive HMX and molecule D outperforms HMX. According to the quantitative standard of energetics and stability as high energy density materials, molecule D essentially satisfies this requirement. These results provide basic information for molecular design of novel high energetic density materials. Copyright © 2012 John Wiley & Sons, Ltd.     

Theoretical study on alkyne-linked carbazole polymers for blue-light multifunctional materials

This paper studied poly[(3,6-di-tert-butyl-N-hexadecyl-1,8-carbazolylene) butadiynylene] (P1), butadiynylene-linked poly (3,6-carbazole) (P2) and butadiynylene-linked poly (2,7-carbazole) (P3) through the theoretical measurements with Gaussian 03 program package. To investigate the relationship between structures and properties of these multifunctional electroluminescent materials, their geometrical structures of ground and excited-states were optimized by B3LYP/6-31G (d) and CIS/6-31G (d) methods, respectively. The lowest excitation energies (E_g's), and the maximum absorption and emission wavelengths of these polymers were calculated by time-dependent density functional theory methods (TD-DFT). The important parameters for luminescent materials were also predicated including the ionization potentials (I_p's) and electron affinities (E_a's). The calculated results show that the highest-occupied molecular orbital (HOMO) energies lift about 0.27-0.49 eV compared to N,N′-bis(naphthyl)-N,N′-diphenyl-1,1′-biphenyl-4,4′-diamine (NPB), suggesting the significant improved hole-accepting and transporting abilities. In addition, substitution of alkyne for carbazole resulted in a narrow band gap and a red shift of both the absorption and emission peaks. Through above calculations, it is evidenced that these polymers can be considered as candidates for excellent OLEDs with good hole-creating abilities and high blue-light emission.     

Theoretical calculations for neighboring group participation in gas‐phase elimination kinetics of 2‐hydroxyphenethyl chloride and 2‐methoxyphenethyl chloride

Theoretical calculation of the kinetics and mechanisms of gas‐phase elimination of 2‐hydroxyphenethyl chloride and 2‐methoxyphenethyl chloride has been carried out at the MP2/6‐31G(d,p), B3LYP/6‐31G(d,p), B3LYP/6‐31 + G(d,p), B3PW91/6‐31G(d,p) and CCSD(T) levels of the theory. The two substrates undergo parallel elimination reactions. The first process of elimination appears to proceed through a three‐membered cyclic transition state by the anchimeric assistance of the aromatic ring to produce the corresponding styrene product and HCl. The second process of elimination occurs through a five‐membered cyclic transition state by participation of the oxygen of o‐OH or the o‐OCH₃ to yield in both cases benzohydrofuran. The B3PW91/6‐31G(d,p) method was found to be in good agreement with the experimental kinetic and thermodynamic parameters for both substrates in the two reaction channels. However, some differences in the performance of the different methods are observed. NBO analysis of the pyrolysis of both phenethyl chlorides implies a C? Cl bond polarization, in the sense of C^δ+…Cl^δ?, which is a rate‐determining step for both parallel reactions. Synchronicity parameters imply polar transition states of these elimination reactions. Copyright © 2009 John Wiley & Sons, Ltd.     

Joint theoretical and experimental study of the gas‐phase elimination kinetics of tert‐butyl ester of carbamic,N, N‐dimethylcarbamic,N‐hydroxycarbamic acids and 1‐(tert‐butoxycarbonyl)‐imidazole

The gas‐phase elimination kinetics of the title compounds were carried out in a static reaction system and seasoned with allyl bromide. The working temperature and pressure ranges were 200–280 °C and 22–201.5 Torr, respectively. The reactions are homogeneous, unimolecular, and follow a first‐order rate law. These substrates produce isobutene and corresponding carbamic acid in the rate‐determining step. The unstable carbamic acid intermediate rapidly decarboxylates through a four‐membered cyclic transition state (TS) to give the corresponding organic nitrogen compound. The temperature dependence of the rate coefficients is expressed by the following Arrhenius equations: for tert‐butyl carbamate logk₁ (s^?1) = (13.02 ± 0.46) – (161.6 ± 4.7) kJ/mol(2.303 RT)^?1, for tert‐butyl N‐hydroxycarbamate logk₁ (s^?1) = (12.52 ± 0.11) – (147.8 ± 1.1) kJ/mol(2.303 RT)^?1, and for 1‐(tert‐butoxycarbonyl)‐imidazole logk₁ (s^?1) = (11.63 ± 0.21)–(134.9 ± 2.0) kJ/mol(2.303 RT)^?1. Theoretical studies of these elimination were performed at Møller–Plesset MP2/6‐31G and DFT B3LYP/6‐31G(d), B3LYP/6‐31G(d,p) levels of theory. The calculated bond orders, NBO charges, and synchronicity (Sy) indicate that these reactions are concerted, slightly asynchronous, and proceed through a six‐membered cyclic TS type. Results for estimated kinetic and thermodynamic parameters are discussed in terms of the proposed reaction mechanism and TS structure. Copyright © 2007 John Wiley & Sons, Ltd.     

Pure red emission of dye-doped organic molecules from microcavity organic light emitting diode

Organic red emitting diode was fabricated by using 4-dicyanomethylene-2-methyl-6-[2-(2,3,6,7-tetrahydro-1 H,5H-benzo[ij]quinolizin-8-yl)vinyl]-4H-pyran (DCM)-doped tri-(8-quinolitolato) aluminum (Alq₃) as emitter with the structure of G/ITO/NPB(25 nm)/DCM:Alq₃(55 nm)/Alq₃(20 nm)/LiF (1.2 nm)/Al(84 nm), (glass/indium–tin-oxide/4,4-bis-[N-(1-naphthyl)-N-phenyl-amino]biphenyl, G/ITO/NPB), the wavelength of the maximal emission of which is 615 nm. By introducing cavity to Organic light emitting diode (OLED), we got pure red emitting diode with wavelength of the maximal emission of 621 nm and full-width at half-maximum (FWHM) of 27 nm. As far as we know, it is the best result in the dye-doped organic red emitting diode. We also made a device of G/ITO/NPB(25 nm)/DCM:Alq₃(29 nm)/DCM:PBD(26 nm)/Alq₃(20 nm)/LiF(1.2 nm)/Al(84 nm), in order to compare the performance of Alq₃ with that of 2-(4-biphenylyl)-5-(4-t-butylphenyl)-1,3,4-oxadiazole (PBD) as host material. It was found that the performance of device A is better than that of C both in brightness and color purity,as well as in EL efficiency.     

发光层和空穴传输层对白色电致发光器件性能的影响

利用电子传输性能良好的苯并噻唑螯合锌(Zn(BTZ)₂)作为蓝光层，通过设计不同类型的空穴传输层并试验不同厚度的发光层后，制作了一种最佳厚度的双发光层白色电致发光器件：氧化铟锡(ITO)/N-N′-双(3-甲基苯基)-N-N′-二苯基-1-1′-二苯基-4-4′-二胺(TPD)∶N,N′-二(1-萘基)-N,N′-二苯基-1,1′-联苯-4-4′-二胺(NPB)(1∶0.0 关键词： 厚度 空穴传输层 白光 载流子     

The mechanism of alkaline hydrolysis of amides: a comparative computational and experimental study of the hydrolysis of N‐methylacetamide,N‐methylbenzamide,and acetanilide

Theoretical computations and experimental kinetic measurements were applied in studying the mechanistic pathways for the alkaline hydrolysis of three secondary amides: N‐methylbenzamide, N‐methylacetamide, and acetanilide. Electronic structure methods at the HF/6‐31+G(d,p) and B3LYP/6‐31+G(d,p) levels of theory are employed. The energies of the stationary points along the reaction coordinate were further refined via single point computations at the MP2/6‐31+G(d,p) and MP2/6‐311++G(2d,2p) levels of theory. The role of water in the reaction mechanisms is examined. The theoretical results show that in the cases of N‐methylbenzamide and N‐methylacetamide the process is catalyzed by an ancillary water molecule. The influence of water is further assessed by predicting its role as bulk solvent. The alkaline hydrolysis process in aqueous solution is characterized by two distinct free energy barriers: the formation of a tetrahedral adduct and its breaking to products. The results show that the rate‐determining stage of the process is associated with the second transition state. The entropy terms evaluated from theoretical computations referring to gas‐phase processes are significantly overestimated. The activation barriers for the alkaline hydrolysis of N‐methylbenzamide and acetanilide were experimentally determined. Quite satisfactory agreement between experimental values and computed activation enthalpies was obtained. Copyright © 2008 John Wiley & Sons, Ltd.     

Theoretical design on a new double functional device of 2,2′‐bipyridine‐embedded N‐(9‐pyrenyl methyl)aza‐15‐crown‐5

Theoretical design on a new molecular switch and fluorescent chemosensor double functional device of aza‐crown ether (2,2′‐dipyridine‐embedded N‐(9‐anthraceneyl(pyrenyl)methyl)aza‐15‐crown‐5) was explored. The interactions between ligands and a series of alkaline earth metal cations (Mg²⁺, Ca²⁺, Sr²⁺, and Ba²⁺) were investigated. The fully optimized geometry structures of the free ligands ( L _1, L ₂) and their metal cation complexes ( L ₁/M²⁺, L ₂/M²⁺) were calculated with the B3LYP/6‐31G(d) method. The natural bond orbital analysis, which is based on optimized geometric structures, was used to explore the interaction of L ₁/M²⁺, L ₂/M²⁺ molecules. The absorption spectra of L _1, L ₂, L ₁/M²⁺, and L ₂/M²⁺, and their excited states were studied by time‐dependent density functional theory. A new type molecular device L ₂(2,2′‐dipyridine‐embedded N‐(9‐pyrenyl methyl)aza‐15‐crown‐5) is designed, which not only has the selectivity for Sr²⁺, and construct allosteric switch, but also has fluorescent sensor performance.     

Theoretical and experimental studies on stability of the C‐ON bond in new ketone functionalized N‐alkoxyamines

Three new ketone functionalized N‐alkoxyamines derived from 2,2,6,6‐tetramethylpiperidin‐1‐oxyl (TEMPO) were prepared: N‐(1‐phenylpropyloxy)‐2,2,6,6‐tetramethylpiperidin‐4‐one, 1‐phenyl‐1‐(2,2,6,6‐tetramethylpiperidinoxy)propanone, 1‐phenyl‐1‐(4‐oxo‐2,2,6,6‐tetramethylpiperidinoxy)propanone. The rate constants of C‐ON bonds homolysis in the synthesized alkoxyamines were determined over a range of temperatures via nitroxide‐exchange experiments using HPLC to monitor the concentration. The Arrhenius parameters of homolysis for the investigated alkoxyamines were determined (lnA, E_a). Homolytic bond dissociation energies (BDE) of the C‐ON bond in the synthesized compounds were determined from quantum‐mechanical calculations at the B3‐LYP/6‐31G(d) and BMK/6‐311+G(3df,2p) levels. Ketone functionalization of the alkyl fragment of alkoxyamine in β position dramatically increases the rate constant of homolysis (by a factor of ca. 500 at the temperature of 363 K) suggesting that the new ketone functionalized N‐alkoxyamines should be effective as C‐radical precursor and unimolecular initiators in NMRP at lower temperatures than the alkoxyamines applied earlier. The analyses of natural bond, frontal orbitals and spin distribution indicated that the decrease in the strength of C‐ON bonds in ketone fuctionalized alkoxyamines in the alkyl fragment predominantly originates from a substantially smaller HOMO–LUMO gap and more delocalized spin density in leaving alkyl radicals as compared with unfunctionalized alkoxyamines. Copyright © 2010 John Wiley & Sons, Ltd.     

Theoretical studies on 2‐(5‐amino‐3‐nitro‐1,2,4‐triazolyl)‐3,5‐dinitropyridine (PRAN) and its derivatives

In this work, a set of derivatives of 2‐(5‐amino‐3‐nitro‐1,2,4‐triazolyl)‐3,5‐dinitropyridine (PRAN) with different energetic substituents (?N₃, –NO₂, –NH₂, –NF₂) have been studied at the Becke, three‐parameter, Lee–Yang–Parr/aug‐cc‐pvdz, Becke, three‐parameter, Lee–Yang–Parr/6‐31G(d), Becke, three‐parameter, Perdew 86/6‐31G(d), and Becke three‐parameter, Perdew–Wang 91/6‐31G(d,p) levels of density functional theory. The gas‐phase heats of formation were predicted with isodesmic reactions and the condensed‐phase HOFs were estimated with the Politzer approach. The effects of different functionals and basis sets were analyzed. –N₃ and –NO₂ greatly increase while –NH₂ and –NF₂ slightly decrease heats of formation. An analysis of the bond dissociation energies and impact sensitivity shows that all compounds have good stability. The crystal densities (1.82–2.00 g/cm³) computed from molecular packing calculations are big for all compounds and that of the –NF₂ derivative is the largest. All derivatives have higher detonation velocity and detonation pressure than PRAN. Compounds 3 and 4 (R = NO₂ and NF₂) have better performance than hexahydro‐1,3,5‐trinitro‐1,3,5‐trizine and the performance of 4 is quite close to that of 1,3,5,7‐tetranitro‐1,3,5,7‐tetraazacyclooctane, they are promising candidates of high energy compounds and worth further investigations. Copyright © 2012 John Wiley & Sons, Ltd.     

Density functional theory analysis of a mixed‐ligand iridium compound for multi‐color organic light‐emitting diodes

Electronic states and their energies are calculated for a mixed‐ligand Ir(III) compound, (5‐chloro‐8‐hydroxyquinoline) bis(2‐phenylpyridyl) iridium (called IrQ(ppy)₂‐5Cl) using time‐dependent density functional theory (TDDFT) calculations and are compared with the experimental result. A good agreement is obtained between the calculated and measured absorption spectra. The d‐π_Q* molecular orbital transition gives the lowest‐energy triplet state absorption band. Its energy is estimated as 1.84 eV (671 nm), which is close to the absorption band position of 1.86 eV (666 nm) observed for IrQ(ppy)₂‐5Cl doped in 4,4′‐N,N′‐dicarbazole‐biphenyl (CBP) host and of 1.88 eV (660 nm) observed for IrQ(ppy)₂‐5Cl doped in polystyrene (PS). The second triplet state absorption band is caused by d‐π_ppy transition. Its position is calculated as 2.51 eV (494 nm). The dipole moment is estimated as 3.45 D, which is lower than the dipole moment of fac‐Ir(ppy)₃. This is understood by a reduced charge transfer between Ir(III) and quinoline ligand. Copyright © 2008 John Wiley & Sons, Ltd.     

Basicity of trifluoromethylsulfonylformamidines. DFT and FTIR study and NBO analysis

The effect of the electron–acceptor substituent CF₃SO₂ at the imine nitrogen atom on the basicity and the electron distribution in N,N‐alkylformamidines ( 1 , 2 , 3 , 4 , 5 ) was studied experimentally by the FTIR spectroscopy and theoretically at the DFT (B3LYP/6‐311+G(d,p)) level of theory, including the natural bond orbital (NBO) analysis. The calculated proton affinities of the imine nitrogen atom and the sulfonyl oxygen (PA_N′ and PA_O) depend on the atomic charges, the C?N′ and N′―S bond polarity and on the energy of interaction of the amine nitrogen and the oxygen lone pairs with antibonding π* and σ*‐orbitals. The basicity of the imine nitrogen atom is increased with the increase of the electron‐donating power of the substituent at the amine nitrogen atom due to stronger interaction n_N → π*_C?N′, but is decreased for the electron‐withdrawing groups MeSO₂ and CF₃SO₂ at the imine nitrogen atom in spite of the increase of this conjugation. Protonation of ( 1 , 2 , 3 , 4 , 5 ) in CH₂Cl₂ solution in the presence of CF₃SO₃H occurs at the imine nitrogen atom, while the formation of hydrogen bonds with 4‐fluorophenol takes place at the sulfonyl oxygen atom, whose basicity is lower than that of N,N′‐dimethylmethanesulfonamide but higher than of N,N′‐dimethyltrifluoromethanesulfonamide. Copyright © 2015 John Wiley & Sons, Ltd.     

A combined experimental and theoretical study of the alkylation of 3,5‐dithioxo‐[1,2,4]triazepines

The chemo‐ and regioselective alkylation reactions of 3,5‐dithioxo[1,2,4]triazepine 1 in a basic medium with α,ω‐dibromoalkanes 2a – c , Br(CH₂)_nBr (n = 1–3), are studied experimentally and theoretically. These alkylations, which occur at the thioxo sulfur atom in position 5, afford mainly 5‐bromomethylthio‐2,7‐dimethyl‐ 2,3‐dihydro‐ 4H[1,2,4]triazepin‐3‐one 3 for n = 1, 6,8‐dimethyl‐5‐thioxo‐2,3,4,5‐tetrahydro‐6H[1,3]thiazolo[4,5‐d][1,2,4]triazepine 4 for n = 2 and 7,9‐dimethyl‐6‐thioxo‐2,3,4,5,6,7‐hexahydro[1,3]thiazino [4,5‐d][1,2,4]triazepine 5 for n = 3. Theoretical calculations have been carried out at the B3LYP/6‐31G* and B3LYP(benzene)/6‐311+G*//B3LYP/6‐31G* levels, in order to rationalize the experimental observations. Both chemo‐ and regio‐selectivities of the alkylation reactions are analyzed. Copyright © 2008 John Wiley & Sons, Ltd.     

Reduced hole loss in organic light emitting diode incorporating two p-doped hole transport layers

The hole-injecting structure of 15 nm MoO₃-doped 4,4-N,N-bis [N-1-naphthyl-N-phenyl-amino]biphenyl (NPB:MoO₃)/5 nm MoO₃-doped 4,4′-N,N′-dicarbazole-biphenyl (CBP:MoO₃) has been used in organic light emitting diodes (OLEDs). It was found that a device using the 15 nm NPB:MoO₃/5 nm CBP:MoO₃/NPB combination was superior to one adopting the 20 nm NPB:MoO₃/NPB combination due to two major causes: the NPB:MoO₃/CBP:MoO₃ interface is a quasi-ohmic contact, and the hole transport barrier from CBP:MoO₃ to NPB is smaller than that from NPB:MoO₃ to NPB; moreover, it outperformed the device employing the 20 nm CBP:MoO₃/NPB combination, mostly because of the higher conductivity of NPB:MoO₃ compared to CBP:MoO₃. We demonstrate that using a structure resulting from uniting two p-doped hole transporters is a beneficial, simple method of achieving an improved trade-off between high conductivity and small hole transport barrier, thereby leading to a significantly reduced ohmic loss in the hole current conduction in the OLEDs, relative to the single p-doped layers.     

Thermal reaction of electron deficient 4‐oxo‐4H‐pyrazole 1,2‐dioxide with cycloheptatriene: the first examples of the formation of an endo‐[4π + 6π]‐cycloadduct and an intramolecular 1,3‐dipolar reaction leading to a heterocage

The reaction of 3,5‐bis(methoxycarbonyl)‐4‐oxo‐4H‐pyrazole 1,2‐dioxide (1a) with 1,3,5‐cycloheptatriene (2b) gave a mixture of the novel endo‐[4 + 6]‐cycloadduct (4ab), anti‐exo‐[4 + 2]‐cycloadduct (5ab), and the heterocage (6ab) derived from the intramolecular 1,3‐dipolar cycloaddition reaction of the syn‐endo‐[4 + 2]‐cycloadduct. Analogous endo‐[4 + 6] selectivity in 1,3‐dipolar cycloadditions has not been reported previously. The X‐ray analysis indicates that 6ab has a very long N_sp3–N_sp3 bond distance of 1.617(4) Å. The cycloaddition behaviour is discussed on the basis of transition‐state structures optimized at the B3LYP/6‐31G(d) level of theory, from which predictions of the peri‐, regio‐, and stereoselectivities agreed well with the experimental results. Copyright © 2012 John Wiley & Sons, Ltd.