Electrochemical properties and radical anions of carbocycle‐fluorinated quinoxalines and their substituted derivatives

Electrochemical reduction (ECR) and oxidation (ECO) of 5,6,7,8‐tetrafluoroquinoxaline ( 1 ) and its derivatives bearing various substituents R (7‐H ( 2 ), 7,8‐H₂ (3 ), 6‐CF₃ ( 4 ), 6‐Cl ( 5 ), 5,7‐Cl₂ ( 6 ), 5‐NH₂ ( 7 ), 6‐OCH₃ ( 8 ), 6,7‐(OCH₃)₂ ( 9 ), 6,7,8‐(OCH₃)₃ ( 10 ), 5,6,7,8‐(OCH₃)₄ ( 11 ), 6‐OCH₃,7‐N(CH₃)₂ ( 12 ), 6‐N(CH₃)₂ ( 13 ), 6,7‐(N(CH₃)₂)₂ ( 14 ), 5,6,7‐(N(CH₃)₂)₃ ( 15 ), and 7,8‐cyclo‐(=CF‐CF = CF‐CF=) ( 16 )) in the carbocycle have been studied by cyclic voltammetry in MeCN. For 1 – 4 and 7 – 15 , the first reduction peaks have been found to be 1‐electron and reversible, thus corresponding to the formation of their radical anions (RAs), which are long lived at 295 K except those of 4 – 6 and 15 , 16 . Irreversible hydrodechlorination has been observed for 5 and 6 at the first step of their ECR confirmed by EPR detection of corresponding RAs of 2 and 5,7‐H₂ derivative of 1 ( 17 ) at the next steps. Electrochemically generated RAs of 1 – 3 , 7 – 14 , and 17 have been characterized in MeCN by EPR spectroscopy together with DFT calculations at the (U)B3LYP/6‐31 + G(d) level of theory using PCM to describe the solvent. A noticeable alternation of spin density on the –NCCN– moiety of quinoxaline has been observed for all RAs possessing R‐substitution asymmetry. The comparative electron‐accepting ability of 1 – 15 has been analyzed in terms of their experimental reduction peak potentials and the (U)B3LYP/6‐31 + G(d)‐calculated gas‐phase first adiabatic electron affinities (EAs). The differences in electron transfer solvation energies for 1 – 15 have been evaluated on the basis of ECR peaks' potentials and calculated gas‐phase EAs. The ECO of 1 – 5 and 7 – 14 has been found to be irreversible.     

Evolution and defect analysis of vertical graphene nanosheets

We report catalyst‐free direct synthesis of vertical graphene nanosheets (VGNs) on SiO₂/Si and quartz substrates using microwave electron cyclotron resonance – plasma enhanced chemical vapor deposition. The evolution of VGNs is studied systematically at different growth stages. Raman analysis as a function of growth time reveals that two different disorder‐induced competing mechanisms contributing to the defect band intensity. The VGNs grown on SiO₂/Si substrates predominantly consists of both vacancy‐like and hopping defects. On the other hand, the VGNs grown on quartz substrates contain mainly boundary‐like defects. X‐ray photoemission spectroscopy studies also corroborate Raman analysis in terms of defect density and vacancy‐like defects for the VGNs grown on SiO₂/Si substrates. Moreover, the grown VGNs exhibit a high optical transmittance from 95% to 78% at 550 nm and the sheet resistance varies from 30 to 2.17 kΩ/sq. depending on growth time. Copyright © 2014 John Wiley & Sons, Ltd.     

Micro‐Raman spectroscopic characterization of a tunable electrochromic device for application in smart windows

An asymmetric electrochromic (EC) device based on an active EC tungsten oxide–titanium oxide (WO₃–TiO₂) layer was constructed. The EC active layer consisted predominantly of monoclinic WO₃ nanocrystallites with a minor additional component of hexagonal WO₃ and amorphous TiO₂. Detailed micro‐Raman spectroscopic studies of the intercalation and deintercalation of lithium in the EC active layer of the EC device as a function of the applied voltage were performed. Three significant structural stages occur upon intercalating Li into the WO₃–TiO₂ layer when coloration potentials of 1.0, 1.5, 2.0, and 3.0 V are applied to the EC device. In the first stage (applied potential of 1.0 V), the m‐Li_x WO₃ phase is retained. In the second stage, (applied potential of 1.5 and 2.0 V) the m‐Li_x WO₃ transforms to a tetragonal phase. In the third stage, (applied potential of 3.0 V) the Raman spectrum exhibits no spectral bands, showing that Li_x WO₃ has attained the highest‐symmetry cubic phase. This phase sequence is confirmed by the X‐ray diffraction (XRD) measurement. These phase transitions can be reversed and, upon complete deintercalation, m‐WO₃ with traces of h‐WO₃ is recovered. Optical transmission studies were performed in conjunction with Raman and XRD studies. A shift of the optical transmittance peak position from 639 to 466 nm and reduction in the width of the transmittance curve with increasing applied potential opens up the possibility of smart window applications for the nanocrystalline WO₃‐based EC device. Copyright © 2008 John Wiley & Sons, Ltd.     

Raman spectra and phase composition of MnGeO3 crystals

MnGeO₃ single‐crystal samples have been synthesized by optical zonal melting and spontaneous crystallization. X‐ray crystal analysis showed the first sample to be a two‐phase one with phase ratio as follows: 17% – monoclinic C2/c, and 83% – orthorhombic Pbca; the phase ratio of the second sample was unknown. Raman spectra have been produced for these samples. Lattice dynamics has been simulated and polarization dependencies of lines' intensities have been analyzed to interpret experimental Raman spectra and to attribute lines to the spectra of monoclinic and orthorhombic phases. Copyright © 2015 John Wiley & Sons, Ltd.     

Transmittance anomalies of a ring with lead-positional asymmetry

We examine the anomalous behavior of the transmittance through a one-dimensional ring having two branches of different lengths, as determined by the lead positions. Jumps in the transmittance phase are occurring in correspondence to both (a) zeros in the transmission at the eigenstates of the isolated ring and (b) destructive interference events. It is also found that when the ratio of the branch lengths is given by p/q satisfying p + q = 0(mod 4), the two characteristic zeros merge into a single point and the transmittance phase becomes identical to the so-called Friedel phase. Received 7 June 2002 / Received in final form 11 December 2002 Published online 4 June 2003 RID="a" ID="a"e-mail: juyeon.yi@physik.uni-regensburg.de     

Photoluminescence and transmittance of CdS1−xTex thin films

CdS_1?xTe_x thin films were prepared by first producing CdS:In thin films by the spray pyrolysis (SP) technique and then annealing the films in the presence of Te vapor in nitrogen atmosphere. X-ray diffraction (XRD) measurements showed that the films are polycrystalline with mixed (cubic and hexagonal) structure. Transmittance measurements were recorded at room temperature in the wavelength range 400–1100 nm. The first derivative of the absorbance – which was deduced from the transmittance – was calculated and used to find the values of the bandgap energy. The presence of two minima in the first derivative curves was interpreted by the presence of a mixed (hexagonal and cubic) phase in accordance with the XRD measurements. The photoluminescence was recorded at T=60 K and a deconvolution peak fit was performed for each spectrum. The dependence of the PL spectra on the tellurium content of the films is obvious through the number, position and amplitude of the peaks in the different bands.     

基于近红外漫反射与漫透射光谱的玉米单倍体鉴别比较研究

使用JDSU公司的MicroNIR1700型微型近红外光谱仪,研究了适合进行单籽粒玉米单倍体鉴别的光谱测量方法。基于近红外光谱定性分析技术,比较了漫反射和漫透射两种情况下玉米单倍体鉴别的效果。光谱数据经过预处理后,采用PLS＋OLDA特征提取算法,应用SVM建立玉米单倍体鉴别模型,分别统计漫反射和漫透射实验条件下,鉴别模型的正确识别率。在微型光谱仪内置光源漫反射的光谱测量方式下,不分胚面朝向,玉米单倍体籽粒平均识别率低于60%,不能有效鉴别玉米单倍体和多倍体。而采用外置光源对籽粒进行漫透射光谱测量方式,获得了平均正确识别率为93.2%的鉴别效果,并且模型稳定性好。实验结果表明,漫反射光谱仅能获得玉米籽粒表层信息,因此玉米籽粒胚面朝向严重影响漫反射光谱鉴别单倍体种子的效果;而漫透射光谱可以实现分析光程纵深信息全累加,能够得到样品内部的信息,因此对胚面朝向不敏感,能够有效地对随机摆放的玉米单倍体和多倍体进行识别。近红外方法能快速、无损地鉴别单倍体,并且微型光谱仪采集速度快,成本低,为实现实用化的自动鉴别提供了条件。     

Layer‐by‐layer AuCl3 doping of stacked graphene films

We investigated the effect of layer‐by‐layer AuCl₃ doping on the electrical and optical properties of stacked graphene films. Graphene grown by the chemical‐vapor deposition method on a Cu‐foil was chemically doped by AuCl₃ solution with a concentration of 20 mM. Eight different configurations were prepared and analyzed by using four‐point probe measurements, optical transmittance measurements, scanning electron microscopy, and micro‐Raman spectroscopy to compare the optical and electrical characteristics of the different graphene samples. In our study, the top‐layer doping method was very effective because better performances considering both sheet resistance and optical transmittance were observed from the configurations with the top‐layer doped. (© 2014 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Trifluoromethanesulfonamide: X‐ray single‐crystal determination and quantum chemical calculations

The X‐ray single‐crystal structure of 1,1,1‐trifluoromethanesulfonamide (triflamide) CF₃SO₂NH₂, which is the ancestor of a large family of its derivatives, has been determined. The crystal structure is composed of infinite layers with an interlayer distance of 3.4 Å. Geometry optimization at the Møller‐Plesset (MP2) and density functional theory (DFT) level showed the calculated bond distances to be, as a rule, longer than the experimental ones. A trial to simulate crystal packing effect on the geometrical parameters by calculating the dimer of triflamide in the gas phase failed – the starting X‐ray geometry of the ‘dimeric’ unit with one NH···O=S H‐bond – was optimized to the cyclic dimer with two H‐bonds. However, when the external (crystal) field effect was simulated using the polarizable continuum model, the experimental geometry of the ‘dimeric’ fragment was satisfactorily reproduced. Calculations of the heptamer cluster having the structure of the hexagon with six triflamide molecules in vertices and one in the middle nicely reproduce the X‐ray structure and brings the geometrical parameters closer to the experiment. Copyright © 2015 John Wiley & Sons, Ltd.     

Fluoropolymer‐based clear and white paint coatings composition analysis by X‐Ray fluorescence

A new method for the quantification of organic and inorganic phase fractions was developed for fluoropolymer/acrylic‐blend paints – clear and white paint coatings – on aluminum panels by using wavelength dispersive X‐ray fluorescence spectrometry (WDXRF). The method was developed for clear coat samples (only containing fluoropolymer and acrylic phases) as well as white paint samples by also measuring silica and titanium dioxide levels. Both WDXRF and X‐ray photoelectron spectroscopy (XPS), a surface technique, were investigated. For clear coat samples, we found that WDXRF provided far superior quantitative results to XPS, likely related to the extreme surface sensitivity of XPS, in this case a drawback more than a strength. For white paint samples, the X‐ray fluorescence spectrometry method achieved a relative accuracy typically better than 5% for the organic phases and better than 2% for the inorganic phases, for measurements on 8‐mm diameter samples. Copyright © 2013 John Wiley & Sons, Ltd.     

Finite thickness lens model for self-focusing (defocusing) in Kerr medium

A “finite thickness lens” model for self-focusing (defocusing) in Kerr medium is presented. An on-axis normalization transmittance formula is presented for arbitrary nonlinear phase shift for the finite thickness Kerr medium by introducing a nonlinear ABCD-matrix for the transition of a Gaussian beam from linear to non-linear medium, without complex calculation for the beam radius at the far field aperture. The variation of the peak and valley transmittance difference is found to enhance linearly as the phase shift at the focus increases by increasing the thickness of the medium. If the ratio of the Rayleigh istance divided by the thickness of the medium (d/z0) is constant and small enough, the peak and valley transmittance difference stays constant. Finally, a qualitative formula is presented to express the relationship between the system parameters and the on-axis phase shift at the focus.      

Structural,electronic, and optical properties of doubly ortho‐linked quinoxaline/diphenylfluorene hybrids

The optical and electronic properties of spiro‐fluorene‐dibenzosuberene[d](1,4‐bis(4‐t‐butylphenyl)quinoxaline) 1a , spiro‐fluorene‐dibenzosuberene[d](1,4‐bis(4‐methoxyphenyl)quinoxaline) 1b , spiro‐fluorene‐dibenzosuberene[d](1‐(4‐(N,N‐diphenylamino)‐phenyl)‐quinoxaline) 1c , spiro‐fluorene‐dibenzosuberene[d](1,4‐bis(methylphenylamino)quinoxaline) 1d , spiro‐fluorene‐dibenzosuberene[d](1,4‐bis(methyl‐(4‐methylphenyl)amino)quinoxaline) 1e , spiro‐fluorene‐dibenzosuberene[d](1,4‐bis(methyl‐(4‐methoxyphenyl)amino)quinoxaline) 1f , 5,8‐bis‐(4‐methoxy‐phenyl)‐2,3‐diphenyl‐quinoxaline 1 , and N,N,N',N'‐tetraphenyl‐ 5h‐dibenzo[a,d]cycloheptene‐3,7‐diamine 2 were investigated theoretically in this paper. The doubly ortho‐linked quinoxaline/diphenylfluorene hybrids 1a – 1f show great potential as bipolar materials for the design of optimized organic light‐emitting diodes (OLEDs). Density functional theory (DFT) and ab initio HF were employed to study the geometric and electronic structures of these molecules in the ground state, and ab initio CIS were used to investigate the lowest singlet excited states. The radiative lifetime (τ) and the maximal absorption/emission wavelength of these molecules were calculated within time‐dependent DFT (TDDFT). The results show that the LUMO energies of the bipolar molecules 1a – 1d are all lower than those of 1 and 2 , consequently, the electron‐accepting abilities of 1a – 1d are greatly improved. The HOMO energies of 1c – 1f are all higher than those of 1 and 2 , suggesting that the hole‐creating abilities of 1c – 1f become better. Also, the results reveal that the HOMO and LUMO energies, energy gaps, IP, EA, as well as the maximal absorption/emission spectra can be tuned feasibly by changing the C5‐ and C8‐substituents in the quinoxaline backbone of these molecules. As expected, these materials show different emission spectra varying from 436.11 to 715.47 nm. Copyright © 2010 John Wiley & Sons, Ltd.     

Microwave‐assisted facile synthesis of liquid crystalline non‐symmetrical hexaalkoxytriphenylenes containing a branched chain and their characterization

Two novel series of liquid crystalline non‐symmetrical hexaalkoxytriphenylenes containing a branched alkyl chain have been prepared using microwave dielectric heating. Series 1 contains 2‐ethyl hexyloxy group as the branched chain whereas series 2 contains 3,7‐dimethyl octyloxy as the branched chain along with five normal alkoxy chains. The number of carbon atoms varies from four to eight in the normal alkoxy chains. Mesophase behaviour of the compounds has been characterized by polarizing optical microscopy, differential scanning calorimetry and mesophase structure has been characterized by X‐ray diffractometry. All the compounds show enantiotropic mesophase transitions with columnar hexagonal structure. In series 1 ( 4a – e ) the mesophase range and transition temperatures of all the compounds are lowered as compared to the parent compounds whereas in series 2 ( 5a – e ) the transition temperatures of all the compounds are lowered, mesophase range for lower members are decreased, however, higher members show more mesophase stability. Both melting and clearing temperatures of series 2 ( 5a – e ) show strong odd–even effect. The intercolumnar distance increases as expected for compounds of both the series with increase in alkyl chain length with some degree of interdigitation of the alkyl chains. The intercolumnar distances for the compounds of the series 2 are slightly higher than the compounds of the series 1 . Compound 4c displays homeotropic alignment without using any special technique for alignment of the columnar phase or application of any external force. Copyright © 2007 John Wiley & Sons, Ltd.     

气炮加载实验中光学窗口透射率测量技术及其应用

报道一种用于气炮加载条件的窗口透射率测量技术。该技术将一种激发电压低(4.5 V)、响应时间快(约500 ns)、输出功率稳定的半导体脉冲光源设置在弹丸内部,在碰靶前激发出光,作为照明光源,用于观测透明样品/窗口在加载过程中的透射率变化。将该技术用于石英玻璃冲击透明性研究,发现石英玻璃在经冲击压缩再卸载到水的过程中,其透射率下降了近30%,该结果不支持文献中所给出的液态水压致固化的解释。     

Negative refractive index in the near‐UV from Au‐coated CuCl nanoparticle superlattices

Nanoparticle superlattices consisting of CuCl spheres coated with a gold (Au) nanoshell are shown to exhibit negative index of refraction in the near‐UV regime. These predictions are based on calculations of the effective refractive index by use of the extended Maxwell–Garnett theory. The results for the refractive index are supplemented by multiple‐scattering calculations of light‐transmittance curves from finite slabs of nanoparticle superlattices. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Two-zone pupil filters

The performance of pupil filters consisting of two zones each of constant complex amplitude transmittance is investigated. For filters where the transmittance is real, different classes of potentially useful filter are identified and optimized. These include leaky filters with an inner zone of low amplitude transmittance, pure phase filters with phase change of π, and equal area filters. The first of these minimizes the relative power in the outer rings for a given axial resolution, the second maximizes the Strehl ratio for a given transverse resolution, and the third minimizes the relative power in the outer rings for a given transverse resolution. Complex filters can give an axially shifted maximum in intensity: the performance parameters calculated relative to the true focus are investigated for some different classes of filter, but filters with phase change not equal to π are found to give inferior performance to the real value filters.     

Enhanced Fröhlich interaction of semiconductor cuprous oxide films determined by temperature‐dependent Raman scattering and spectral transmittance

Anomalous low temperature behaviors in cuprous oxide (Cu₂O) film grown on quartz substrate have been investigated by temperature‐dependent Raman and transmittance spectra. The longitudinal optical components of two Γ₁₅‐ phonon modes become sharper and more intense at a low temperature. It can be found that the highest‐order electronic transition located at 6.4 eV exhibits a minimum transmittance near 200 K. Correspondingly, the variations from phonon intensity ratios reveal obvious anomalies with the decreasing temperature, indicating the existence of strong electron–phonon coupling mediated by Fröhlich interaction in the Cu₂O films below the temperature of 200 K. Copyright © 2012 John Wiley & Sons, Ltd.     

Analysis of transmittance enhancement for a slab lens formed by sub-wavelength holes array on the metallic film

By investigating the transmittance and phase characteristics of the square holes on the metallic film, we find that the transmittance fluctuates with center distance between holes and appears resonant peaks, which attributes to the surface wave enhanced transmission phenomenon while the corresponding phase retardation through holes keeps constant. Based on this phenomenon, the slab lens can be optimized to a high transmittance by modulating the center distance of the holes. Design results show that the light intensity values at the focal spot of the slab lens can be enhanced from 3 to 14.5 in intensity scale when the center distance changes from 1.25λ to 0.95λ.     

近红外消偏振分光膜设计近红外消偏振分光膜设计

大角度倾斜入射时,光学薄膜表现出强烈的偏振效应。入射光S分量和P分量的反射率和透射率曲线,以及反射或透射引起的两个分量的相位变化都不再相同,彼此有一定的偏振分离。通过对产生偏振效应内在原因的分析,采用一个在近红外波段对于45倾斜入射光的S分量和P分量等效导纳非常接近的膜系结构,结合单纯形法优化算法,设计得到一个1 500～1 600 nm范围内反射率都是50％的近红外消偏振分光膜。结果显示,在45入射时,S分量和P分量的反射率曲线偏振分离小,反射和透射引起的相位变化也控制在很小范围。     

A Simple Hydrothermal Method for the Growth of ZnO Crystals

ZnO microstructures have been grown from zinc chloride (ZnCl₂) and ammonia solution at 100 °C for 1 – 24 hours. X‐ray diffraction, scanning electron microscope and field‐emission scanning microscope were utilized to investigate the structural properties and morphology of the ZnO crystals. Structural investigations show that phase‐pure hexagonal structure ZnO has been successfully synthesized, and the hexagonal structure ZnO can be achieved in solutions with an appropriate range of concentrations. Under our experimental conditions, several different morphologies of ZnO structures were obtained, including flower‐like and bar flower‐like. The relationship between the morphology and experimental conditions are discussed.