Two fluoro compounds of main group elements: Synthesis,characterization, theoretical and spectroscopic study

Two new compounds of fluorine: (C₂H₅)₄N[I₂F] and (C₂H₅)₄N[Br₂F], have been easily synthesized in a nearly quantitative by a direct reaction of (C₂H₅)₄NF, I₂ and Br₂. The products were isolated and characterized by elemental analysis and spectroscopic methods such as: Fourier transform infrared spectroscopy (FTIR) and ultraviolet-visible spectroscopy (UV-Vis). These compounds have been studied computationally with the Scalar ZORA relativistic level of theory using the ADF program package. The molecular parameters, and vibrational spectra were calculated. The excitation energies were found by timedependent perturbation density functional theory (TD-DFT). Molecule optimization, frequencies and excitation energies were calculated with standard Slatertype-orbital (STO) basis sets with triple-zeta quality double plus polarization functions (TZ2P) for all atoms. The FTIR, UV-Vis spectra and assignment of principal transitions and total density of state (TDOS) were extracted using the GaussSum 2.2 program. The comparison between experimental and calculated values showes that the experimental results correlate well with the predicted data.     

Molecular design of ambipolar redox-active molecules II: closed-shell systems

This mini-review highlights key structural features that should be taken into account when creating ambipolar redox-active closed-shell metal-free molecules. This type of compound is strongly required for the fabrication of all-organic ‘poleless’ batteries and semiconductors. The suggested strategies aimed at stabilization of both oxidized (cationic) and reduced (anionic) redox-states are based on the comprehensive analysis of the most successful structures taken from the recent publications.     

Holography beyond conformal invariance and AdS isometry?

Journal of Experimental and Theoretical Physics - We suggest that the principle of holographic duality be extended beyond conformal invariance and AdS isometry. Such an extension is based on a...     

Reactions of Aryl Benzoates with Potassium Aryloxides: Solvent Effects on Reaction Pathway and Kinetics

Temperature dependences of the relative reactivity of potassium aryloxides XC₆H₄O^?K⁺ toward 2,4‐dinitrophenyl benzoate in 50 mol% dimethylformamide (DMF)–50 mol% H₂O mixture have been studied using the competitive reactions technique. Correlation analyses of the relative rate constants k_X/k_H and differences in the activation parameters (ΔΔН^≠ and ΔΔS^≠) of the competitive reactions have revealed the existence of two isokinetic series of the reactions of 2,4‐dinitrophenyl benzoate with potassium aryloxides with electron‐donating substituent (EDS) and electron‐withdrawing substituent (EWS), respectively. We have investigated the effect of the substituent X on the activation parameters for each isokinetic series and concluded that the mechanism of the reactions of 2,4‐dinitrophenyl benzoate with potassium aryloxides XC₆H₄O^?K⁺ in 50 mol% DMF–50 mol% H₂O mixture is the same as in DMF. Analysis of the obtained data with using the method of two‐dimensional reaction coordinate diagram leads to the conclusion that the variation of the solvent from DMF to 50 mol% DMF–50 mol% H₂O mixture affects the reaction pathway. The rate constant k_X for the reaction of 3‐nitrophenyl benzoate with potassium 4‐methoxyphenoxide and the relative rate constants k_X/k_H for the reaction of 3‐nitrophenyl benzoate with potassium aryloxides XC₆H₄O^?K⁺ with EDS were measured in 50 mol% DMF–50 mol% H₂O mixtures at 25°C, and it has been shown that the addition of water to DMF does not change the mechanism but slows down these reactions.     

3D‐morphology reconstruction of nanoscale phase‐separation in polymer memory blends

In many organic electronic devices functionality is achieved by blending two or more materials, typically polymers or molecules, with distinctly different optical or electrical properties in a single film. The local scale morphology of such blends is vital for the device performance. Here, a simple approach to study the full 3D morphology of phase‐separated blends, taking advantage of the possibility to selectively dissolve the different components is introduced. This method is applied in combination with AFM to investigate a blend of a semiconducting and ferroelectric polymer typically used as active layer in organic ferroelectric resistive switches. It is found that the blend consists of a ferroelectric matrix with three types of embedded semiconductor domains and a thin wetting layer at the bottom electrode. Statistical analysis of the obtained images excludes the presence of a fourth type of domains. The criteria for the applicability of the presented technique are discussed. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 1231–1237     

Simulation of dependence of the cross section of deuterons beam fragmentation into cumulative pions and protons on the mass of the target nucleus

Physics of Atomic Nuclei - We have studied the mechanisms influencing production of cumulative pions and protons in the fragmentation of the incident deuterons into cumulative pions and protons...     

Control over Nanostructures and Associated Mesomorphic Properties of Doped Self‐Assembled Triarylamine Liquid Crystals

We have synthesized a series of triarylamine‐cored molecules equipped with an adjacent amide moiety and dendritic peripheral tails in a variety of modes. We show by ¹H NMR and UV/Vis spectroscopy that their supramolecular self‐assembly can be promoted in solution upon light stimulation and radical initiation. In addition, we have probed their molecular arrangements and mesomorphic properties in the bulk by integrated studies on their film state by using differential scanning calorimetry (DSC), variable‐temperature polarizing optical microscopy (VT‐POM), variable‐temperature X‐ray diffraction (VT‐XRD), and atomic force microscopy (AFM). Differences in the number and the disposition of the peripheral tails significantly affect their mesomorphic properties associated with their lamellar‐ or columnar‐packed nanostructures, which are based on segregated stacks of the triphenylamine cores and the lipophilic/lipophobic periphery. Such structural tuning is of interest for implementation of these soft self‐assemblies as electroactive materials from solution to mesophases.     

Anisotropic Elastic-Viscoplastic Properties at Finite Strains of Injection-Moulded Low-Density Polyethylene

Injection-moulding is one of the most common manufacturing processes used for polymers. In many applications, the mechanical properties of the product is of great importance. Injection-moulding of thin-walled polymer products tends to leave the polymer structure in a state where the mechanical properties are anisotropic, due to alignment of polymer chains along the melt flow direction. The anisotropic elastic-viscoplastic properties of low-density polyethylene, that has undergone an injection-moulding process, are therefore examined in the present work. Test specimens were punched out from injection-moulded plates and tested in uniaxial tension. Three in-plane material directions were investigated. Because of the small thickness of the plates, only the in-plane properties could be determined. Tensile tests with both monotonic and cyclic loading were performed, and the local strains on the surface of the test specimens were measured using image analysis. True stress vs. true strain diagrams were constructed, and the material response was evaluated using an elastic-viscoplasticity law. The components of the anisotropic compliance matrix were determined together with the direction-specific plastic hardening parameters.