Conformational analysis of 4,4‐dimethyl‐4‐silathiane and its S‐oxides

4,4‐Dimethyl‐4‐silathiane and its S‐oxides [n = 0 ( 1 ), 1 ( 2 ), 2 ( 3 )] were studied experimentally by variable temperature dynamic NMR spectroscopy down to 103 K and the frozen ring inversion was revealed for all three compounds. The barriers for the degenerate ring inversion in 1 and 3 were measured to be 4.8 and 5.0 kcal/mol at the coalescence temperatures of 111 and 116 K, respectively, and practically coincide with the calculated barriers of 4.60 kcal/mol in 1 and 4.46 kcal/mol in 3 . The frozen equilibrium mixture 2‐ax/2‐eq contains 37% of the 2‐ax and 63% of the 2‐eq conformer. The ring inversion barrier proved to be ca. 4.8 kcal/mol. Calculations at the B3LYP/6‐311+G(d,p) level of theory showed the 2‐ax conformer to be 0.90 kcal/mol more stable than the 2‐eq conformer in the gas phase whereas in solution the relative stability of the conformers calculated using the PCM model at the same level of theory is inverted to become 0.19 (in CHCl₃) or 0.36 kcal/mol (in DMSO) in favor of the 2‐eq conformer. The chair–chair interconversion mechanism of sulfoxide 2 includes two intermediate energetically equivalent 1,4‐twist forms and the 2,5‐boat transition state: 2‐ax (chair) ? 2 (1,4‐twist) ? [ 2 (2,5‐boat)]^≠ ? 2 (1,4‐twist) ? 2‐eq (chair). The calculated ring inversion barriers are 5.1 ( 2‐ax → 2‐eq ) and 4.2 kcal/mol ( 2‐eq → 2‐ax ) in the gas phase, and 4.03 and 4.22 kcal/mol, respectively, in chloroform. Copyright © 2011 John Wiley & Sons, Ltd.     

Determination of sulfoxide bond dissociation enthalpies of dibenzothiophene S‐oxide derivatives with computational methods

Photodeoxygenation of dibenzothiophene S‐oxide (DBTO) has been suggested as a clean way to generate atomic oxygen in solution. Sulfoxide bond dissociation enthalpies (BDEs) are important to the quantum yield and mechanism of this photodeoxygenation. In this study, BDE of substituted DBTO molecules with various functional groups were determined using M062X/aug‐cc‐pV(T + d)Z and MP2/aug‐cc‐pV(T + d)Z levels of theory. The sulfoxide BDE was determined using an isodesmic reaction. The observed effect of substitution was that functional groups with negative σ_para values (electron donating) strengthen the sulfoxide bond and that substituents with positive σ_para values (electron withdrawing) weaken the sulfoxide bond. The Mulliken charge on sulfur for DBTO and the corresponding dibenzothiophene were identified as a suitable indicator of the predicted S–O BDE. Moreover, steric and hydrogen bonding interactions were found to affect sulfoxide BDE for certain functional groups when located at the 1 or 4 positions of the substituted DBTO. Copyright © 2014 John Wiley & Sons, Ltd.     

Effect of irradiation on ethyl 2‐amino‐4,5,6,7‐tetrahydrobenzo[b]thiophene‐3‐carboxylate: an ESR study

Ethyl 2‐amino‐4,5,6,7‐tetrahydrobenzo[b]thiophene‐3‐carboxylate [C₁₁H₁₅NO₂S] was synthesized by the Gewald method. Its single crystals were grown from an alcohol/ethyl acetate solution at 15 °C and characterized using IR and ¹H‐NMR. These single crystals were irradiated for 72 h at 298 K by a ⁶⁰Co gamma source with a dose speed of 0.864 kGy/h. After irradiation, electron spin resonance (ESR) measurements were carried out to study radiation‐induced radicals in the temperature range from 120 to 450 K. Additionally, for the single crystal, ESR angular dependencies were measured in the xy, xz and yz planes of the substance. This irradiated single crystal was analyzed based on the ESR spectra. Analysis of the spectra revealed that the radical was formed by a C–H bond fission at the carbon end of the substance. It was also observed that the color of the sample changed after irradiation. The hyperfine and g parameters were determined from the experimental spectra. It was inferred from these results that the hyperfine parameters and g value exhibited anisotropic behavior. The average values of these parameters were calculated as follows: g = 2.0088, A_H1=H2 = 20.70 G, A_H3=H4 = 10.80 G, A_Ha = 4.59 G, A_Hb = 3.24 G and, A_N = 6.10 G. Copyright © 2011 John Wiley & Sons, Ltd.     

Electrochemical reduction of 3‐phenyl‐1,2‐benzisoxazole 2‐oxide on boron‐doped diamond

The bioreduction of N‐oxide compounds is the basis for the mode of action of a number of biologically active molecules. These compounds are thought to act by forming a reactive oxygen species through an intracellular reduction and subsequent redox cycling process within the organism. With these results in mind, the preliminary investigation into the electrochemical reduction of the benzisoxazole 2‐oxide ring system was undertaken, with the thought that this class of compounds would reduce in a similar fashion to other N‐oxide heterocycles. The electrochemical reduction of 3‐phenyl‐1,2‐benzisoxazole 2‐oxide on boron‐doped diamond was studied using cyclic and square wave voltammetry as well as controlled potential electrolysis and HPLC for qualitative identification of the reaction products. It was found that the reduction proceeded with an initial quasi‐reversible one‐electron reduction followed by the very fast cleavage of either the endocyclic or exocyclic N–O bond. Subsequent electron transfer and protonation resulted in an overall two‐electron reduction and formation of the 2‐hydroxyaryl oxime and benzisoxazole. These results are analogous to those observed in the electrochemical reduction of other heterocyclic N‐oxides albeit the reduction of the benzisoxazole N‐oxides takes place at a more negative potential. However, these encouraging results warrant further investigation into the reduction potential of substituted benzisoxazole N‐oxides as well as to elucidate and characterize the nature of the intermediate species involved. Copyright © 2014 John Wiley & Sons, Ltd.     

Photochemistry of a 6′‐cyanosubstituted spironaphthooxazine: photo‐induced decay of an open form

Photochemistry of three 6′‐cyanosubstituted spironaphthooxazines (SNO) in ethanol matrices at 77 K was studied by means of ultraviolet (UV) and erythrocyte sedimentation rate (ESR) spectroscopy and quantum chemistry. The quantum yield of the open form photolysis is found to be 0.01–0.02, which is high enough for 77 K. For one of the SNO, the formation of a merocyanine form radical was observed. The radicals were formed by an H atom abstraction from the solvent molecule to the light‐excited merocyanine isomers. The formation of a merocyanine radical represents a new specific channel of photochemically induced degradation of spirooxazines. Copyright © 2011 John Wiley & Sons, Ltd.     

One decade of fully transparent oxide thin‐film transistors: fabrication,performance and stability

We review the history of fully transparent oxide thin‐film transistors. Their performance and stability increased during the past ten years of their existence, thus enabling the design of novel applications in transparent electronics. However, certain disadvantages of the well established leading technology of metal–insulator–semiconductor field‐effect transistors (MISFETs), adapted from the silicon‐based complementary metal–oxide–semiconductor (CMOS) and thin‐film transistor technology, may be overcome by alternative transistor designs like metal–semiconductor field‐effect transistors (MESFETs). We compare the stability of published transparent MISFET with our transparent MESFET (TMESFET) technology against bias stress, towards illumination, at elevated temperatures and long‐term stability.

     

Mechanism and regioselectivity of the 1,3‐dipolar cycloaddition of thiocarbonyl S‐imide with cyclopent‐3‐ene‐1,2‐dione and methoxyethene: a density functional theory approach

A theoretical study on the regioselectivity of 1,3‐dipolar cycloaddition reaction between an uncommon dipole (thiocarbonyl S‐imide) with cyclopent‐3‐ene‐1,2‐dione (DPh1) and methoxyethene (DPh2) has been carried out by means of several theoretical approaches, namely, activation energy, Houk's rule based on the frontier molecular orbital theory and density functional theory (DFT) reactivity indices. The calculations were performed at the DFT‐B3LYP/6‐31G(d) level of theory using GAUSSIAN 09. The present analysis shows that the 1,3‐dipolar cycloaddition of thiocarbonyl S‐imide with DPh1 and DPh2 has normal‐electron demand and inverse‐electron demand character, respectively. Moreover, the results obtained from energetic point view are in agreement with electronic approaches, and the Houk's rule is capable to predict true regioselectivity. Copyright © 2012 John Wiley & Sons, Ltd.     

Nondestructive investigation of interface states in high‐k oxide films on Ge substrate using X‐ray absorption spectroscopy

The unoccupied electronic structures of 5 nm thick high permittivity (k) oxides (HfO₂, ZrO₂, and Al₂O₃) and SiO₂ films on Ge substrates were examined using O K‐edge X‐ray absorption spectroscopy. Comparative studies with those on Si substrates showed contrasts in the conduction bands, which should be due to the formation of interface states. In the Al₂O₃ and SiO₂ films, GeO₂ layers are formed at the interface and they suppress in part the formation of detrimental germanate phases. In contrast, in the HfO₂ and ZrO₂ films, no signature of the Ge‐oxide phase is observed but some germanate phases are expected to prevail, suggesting a degradation of the gate oxide characteristics. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

An analytic method for S‐Expansion involving resonance and reduction

In this paper we describe an analytic method able to give the multiplication table(s) of the set(s) involved in an S‐expansion process (with either resonance or 0_S‐resonant‐reduction) for reaching a target Lie (super)algebra from a starting one, after having properly chosen the partitions over subspaces of the considered (super)algebras. This analytic method gives us a simple set of expressions to find the subset decomposition of the set(s) involved in the process. Then, we use the information coming from both the initial (super)algebra and the target one for reaching the multiplication table(s) of the mentioned set(s). Finally, we check associativity with an auxiliary computational algorithm, in order to understand whether the obtained set(s) can describe semigroup(s) or just abelian set(s) connecting two (super)algebras. We also give some interesting examples of application, which check and corroborate our analytic procedure and also generalize some result already presented in the literature.     

Visible light‐induced diastereoselective E/Z‐photoisomerization equilibrium of the C=C benzofuran‐3‐one‐hydantoin dyad

The diastereoselective photodependent isomerization equilibrium of E/Z‐1,3‐ditolyl‐5‐[3‐oxobenzofuran‐2(3H)‐ylidene]imidazolidine‐2,4‐dione ( 5 ) is reported. Both diastereomers E-5 and Z-5 are stereochemically stable in solid state but show significant photosensibility in solutions of halogenated solvent. The photoisomerization equilibrium of E/Z‐ 5 is therefore deduced from the ¹H NMR profile after visible‐light irradiation of both E-5 and Z-5 samples. The results of the kinetic study, monitored by UV‐HPLC, reveal that the E/Z equilibrium is diastereoselective and photodependent, being the transformation E ? Z proceeding faster than that of Z ? E, and the E/Z ratio at the equilibrium depends on the used solvent, light source, and temperature. Both diastereomers are visible‐light photosensitive tending to coexist together in equilibrium solutions at a determined ratio, which is always in favor of the Z‐product assuming a minimum thermodynamic energy and an increased entropy of the system. Time‐dependent density functional theory calculations suggest that the photoisomerization mechanism proceeds via a conical intersection involving the first‐excited state: Upon irradiation, the E-5 isomer is excited to the S1 potential energy surface, where it relaxes through rotation of the C=C bond and reaches a conical intersection with the ground‐state potential energy surface, thus yielding the Z-5 isomer. Copyright © 2014 John Wiley & Sons, Ltd.     

The metal‐insulator transitions of VO2: A band theoretical approach

The results of first principles electronic structure calculations for the metallic rutile and the insulating monoclinic phase of vanadium dioxide are presented. In addition, the insulating phase is investigated for the first time. The density functional calculations allow for a consistent understanding of all three phases. In the rutile phase metallic conductivity is carried by metal orbitals, which fall into the one‐dimensional band, and the isotropically dispersing bands. Hybridization of both types of bands is weak. In the phase splitting of the band due to metal‐metal dimerization and upshift of the bands due to increased p‐d overlap lead to an effective separation of both types of bands. Despite incomplete opening of the optical band gap due to the shortcomings of the local density approximation, the metal‐insulator transition can be understood as a Peierls‐like instability of the band in an embedding background of electrons. In the phase, the metal‐insulator transition arises as a combined embedded Peierls‐like and antiferromagnetic instability. The results for VO₂ fit into the general scenario of an instability of the rutile‐type transition‐metal dioxides at the beginning of the d series towards dimerization or antiferromagnetic ordering within the characteristic metal chains. This scenario was successfully applied before to MoO₂ and NbO₂. In the compounds, the and bands can be completely separated, which leads to the observed metal‐insulator transitions.     

Semiclassical line broadening calculations,using an ab initio potential energy surface,in Q‐branch and S‐branch of N2 perturbed by H2

In order to improve the accuracy of Raman combustion diagnostics, the broadening coefficients of N₂ perturbed by H₂ for Q‐branch and S‐branch have been calculated by the semiclassical Robert–Bonamy model using an ab initio potential energy surface. The calculations have been performed for a large range of temperatures (from 77 to 800 K) and J rotational quantum numbers (from 0 to 60). This paper shows that our results and their temperature dependence are in good agreement with earlier published experimental and theoretical data. Moreover, our results improve the semiclassical calculations made earlier with an adapted analytical potential. The results, obtained at high temperatures and for a large range of rotational quantum numbers, are presented in order to be implemented for optical diagnostics in combustion media. Copyright © 2012 John Wiley & Sons, Ltd.     

Theoretical studies on the electronic and optical properties of arene‐ versus fluoroarene‐thiophene co‐oligomer

A series of regiochemically varied and core size extension‐modulated arene‐ and fluoroarene‐thiophene co‐oligomers and the unsubstituted sexithiophene α6T were investigated theoretically to explore their electronic and optical properties. These phenylene‐thiophene oligomers show great potential for application in organic light‐emitting diodes (OLEDs), organic diode lasers, and organic thin‐film transistors (OTFTs) because of their feasible tuning of optical and electronic properties by the various structural tunings. Density functional theory (DFT) and the ab initio HF were employed to investigate the geometric and electronic structures of the oligomers in the ground state, and the singles configuration interaction (CIS) methods were used to study the lowest singlet excited state. The lowest excitation energies (E_gs), the radiative lifetime τ, and the maximal absorption/emission wavelength of the oligomers were studied within time‐dependent DFT (TDDFT). All calculations were performed using the 6‐31G(d) basis set. The results show that the HOMOs, LUMOs, energy gaps, ionization potentials (IPs), electron affinities (EAs), and reorganization energies are significantly affected by the various structural tunings in these co‐oligomers, which is important for the improvement of the hole and electron injection into OLEDs. Interestingly, the LUMO energy of 1b , 2b , and 3b is lower than that of α6T and 1a , 2a , 3a by about 0.12 ～ 0.47 eV, indicating that the fluorophenyl‐substitution has significantly improved the electron injection properties of the oligomers. Copyright © 2008 John Wiley & Sons, Ltd.     

Ultra‐thin (002)‐oriented Al‐doped zinc oxide transparent electrode grown on oxygen‐controlled homo‐seed layer

Highly (002)‐oriented Al‐doped zinc oxide (AZO) thin films with the thickness of less than 200 nm have been deposited on an oxygen‐controlled homo‐seed layer at 200 °C by DC magnetron sputtering. With the homo‐seed layer being employed, the full‐width at half maximum (FWHM) of the (002) diffraction peak for the AZO ultra‐thin films decreased from 0.33° to 0.22°, and, the corresponding average grain size increased from 26.8 nm to 43.0 nm. The XRD rocking curves revealed that the AZO ultra‐thin film grown on the seed layer deposited in atmosphere of O₂/Ar of 0.09 exhibited the most excellent structural order. The AZO ultra‐thin film with homo‐seed layer reached a resistivity of 4.2 × 10^–4 Ω cm, carrier concentration of 5.2 × 10²⁰ cm^–3 and mobility of 28.8 cm² V^–1 s^–1. The average transmittance of the AZO ultra‐thin film with homo‐seed layer reached 85.4% in the range of 380–780 nm including the substrate. (© 2014 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

The photoinduced reaction of 2‐iodothiophene in solutions of n‐heptane,dichloromethane and methanol

The photoinduced reaction of 2‐iodothiophene in n‐heptane, dichloromethane and methanol was studied at room temperature from experiments carried out with degassed solutions. The photoproducts of the reaction were mainly thiophene and small amounts of iodine in all three solvents used. The concentration of 2‐iodothiophene decreases throughout photolysis, following a first‐order rate law and the pseudo‐first‐order rate constants were determined in the three solvents used. The photochemistry of the system was quantified determining the quantum yields of 2‐iodothiophene consumption and thiophene formation in n‐heptane solutions. The results show that under the experimental conditions of this research, products deriving only from the reaction of the thienyl radical were observed. To support the experimental results, calculations were performed of the ionization potential of the thienyl radical, electron affinity of the iodine atom and free energy of solvation of the corresponding iodide and carbocation in the different solvents used. Copyright © 2010 John Wiley & Sons, Ltd.     

Electrogenerated chemiluminescence of benzo 15‐crown‐5 derivatives

Novel electrogenerated chemiluminescence (ECL) reagents C1 , C2 , and C3 with high fluorescence quantum yields bearing 15‐crown‐5 moiety have been synthesized and characterized. The photophysical, electrochemical, and ECL characters of these compounds have been studied in a 1:1 (v/v) PhH/MeCN mixed solvent. The ECL intensity is enhanced distinctly with the increase in the fluorescence quantum yield. Their ECL behaviors have been studied using annihilation and co‐reactant methods (tri‐n‐propylamine (TPrA) was used as a co‐reactant), respectively. The stable ECL emissions of compounds C1 – C3 can be ascribed to the typical and simple monomer ECL emission via S‐route. Copyright © 2008 John Wiley & Sons, Ltd.     

Picosecond‐resolved X‐ray absorption spectroscopy at low signal contrast using a hard X‐ray streak camera

A picosecond‐resolving hard‐X‐ray streak camera has been in operation for several years at Sector 7 of the Advanced Photon Source (APS). Several upgrades have been implemented over the past few years to optimize integration into the beamline, reduce the timing jitter, and improve the signal‐to‐noise ratio. These include the development of X‐ray optics for focusing the X‐rays into the sample and the entrance slit of the streak camera, and measures to minimize the amount of laser light needed to generate the deflection‐voltage ramp. For the latter, the photoconductive switch generating the deflection ramp was replaced with microwave power electronics. With these, the streak camera operates routinely at 88 MHz repetition rate, thus making it compatible with all of the APS fill patterns including use of all the X‐rays in the 324‐bunch mode. Sample data are shown to demonstrate the performance.     

Synthesis and rational design of anti‐inflammatory compounds: N‐phenyl‐cyclohexenyl sulfonamide derivatives

The synthesis of (±)‐ethyl 6‐[N‐(2‐chloro‐4‐fluorophenyl)sulfamoyl]cyclohex‐1‐ene‐1‐carboxylate ( 5n ) has been reproduced from a method previously described and served as the background for the preparation of a nitro derivative, potentially useful as an anti‐inflammatory agent. Furthermore, a structure‐based QSAR analysis of a series of N‐arylsulfamoyl congeners derived a highly predictive model for the activities of novel small‐molecule inhibitors of NO and cytokine production, whose preparation may be successfully achieved according to a similar procedure as above. Copyright © 2009 John Wiley & Sons, Ltd.     

On structural and spectroscopic differences between quinoline‐2‐carboxamides and their N‐oxides in the solution and solid state

Intramolecular hydrogen bonding in the primarily and secondarily substituted quinoline‐2‐carboxamides and their N‐oxides has been studied in the solution by multinuclear NMR spectroscopy. Hydrogen bonding patterns and supramolecular arrangement in the solid state have been determined by single crystal X‐ray analysis. In quinoline‐2‐carboxamides weak, nonlinear intramolecular N? H…N hydrogen bond is present, but in the solid state the intermolecular hydrogen bonds and packing forces are the factors that decide on the properties of 3D structures. In quinoline‐2‐carboxamide N‐oxides the most important structural features are the intramolecular hydrogen bonds. Details of different weak interactions and resulting 3D arrangement of molecules are discussed. In the solution, two separate ¹H signals are observed for the primary quinoline‐2‐carboxamides in the range from ca. 5.8 to 8.1 ppm. The chemical shifts of the NH group's proton for studied R′‐quinoline‐2‐R‐carboxamides are in the range from 8.1 to 8.4 ppm. For the N‐oxide of 4‐R′‐quinoline‐2‐carboxamides (R′ = H, Me, OPh, Cl and Br), the values of the proton chemical shifts of the NH group in the range from 10.78 to 11.38 ppm (for primary amides) indicating that this group forms hydrogen bonds with the oxygen of the N‐oxide group. This bond is stronger than the N? H…N bond in quinoline‐2‐carboxamides. For the secondary amide N‐oxides, the δ(NH) values are increasing from 11.25 to 11.77 ppm in the sequence of substituents 4‐Br < 4‐Cl < 4‐H < 4‐Me < 4‐OPh. For 4‐substituted compounds these values depend also on the substituent effect. Copyright © 2009 John Wiley & Sons, Ltd.