Diaryldichalcogenide radical cations

One-electron oxidation of two series of diaryldichalcogenides (C₆F₅E)₂ (13a–c) and (2,6-Mes₂C₆H₃E)₂ (16a–c) was studied (E = S, Se, Te). The reaction of 13a and 13b with AsF₅ and SbF₅ gave rise to the formation of thermally unstable radical cations [(C₆F₅S)₂]˙⁺ (14a) and [(C₆F₅Se)₂]˙⁺ (14b) that were isolated as [Sb₂F₁₁]^– and [As₂F₁₁]^– salts, respectively. The reaction of 13c with AsF₅ afforded only the product of a Te–C bond cleavage, namely the previously known dication [Te₄]²⁺ that was isolated as [AsF₆]^– salt. The reaction of (2,6-Mes₂C₆H₃E)₂ (16a–c) with [NO][SbF₆] provided the corresponding radical cations [(2,6-Mes₂C₆H₃E)₂]˙⁺ (17a–c; E = S, Se, Te) in the form of thermally stable [SbF₆]^– salts in nearly quantitative yields. The electronic and structural properties of these radical cations were probed by X-ray diffraction analysis, EPR spectroscopy, and density functional theory calculations and other methods.     

Adsorption of I2 by Macrocyclic Polyazadithiophenolato Complexes Mediated by Charge‐Transfer Interactions

The macrocyclic complex [Ni₂(L)(OAc)]ClO₄ ( 1 ) adsorbs up to 17 molar equivalents (>270 wt %) of iodine, although it does not exhibit permanent porosity. Vibrational spectroscopic and crystallographic studies reveal that two I₂ molecules are captured by means of thiophenolate→I₂ charge‐transfer interactions, which enable the diffusion and sorption of further I₂ molecules in a polyiodide‐like network. The efficient sorption and desorption characteristics make this material suitable for accommodation, sensing, and slow release of I₂.     

Rheological properties of branched polystyrenes: linear viscoelastic behavior

Oscillatory shear measurements on a series of branched graft polystyrenes (PS) synthesized by the macromonomer technique are presented. The graft PS have similar molar masses (M _w between 1.3×10⁵ g/mol and 2.4×10⁵ g/mol) and a polydispersity M _w /M _n around 2. The molar masses of the grafted side chains M _w,br range from 6.8×10³ g/mol to 5.8×10⁴ g/mol, which are well below and above the critical entanglement molar mass M _c of linear polystyrene. The average number of side chains per molecule ranges from 0.6 to 6.7. The oscillatory measurements follow the time–temperature superposition principle. The shift factors do not depend on the number of branches. The zero-shear viscosities of all graft PS are lower than those of linear PS with the same molar mass, which can be attributed to the smaller coil size of the branched molecules. It is shown that the influence of branching on the frequency dependence of the dynamic moduli is weak for all graft PS that were investigated, which can be explained by the low entanglement density.Electronic Supplementary Material Supplementary material is available for this article at This article has already been published online first (DOI: ). Due to an oversight at the publisher's, this version contained several mistakes. The article is herewith republished in its entirety as a "publisher's erratum".     

Down-flow and horseshoe vortex characteristics of sediment embedded bridge piers

The flow around bridge structures is a recent research topic, given the significance of bridges as basic engineering infrastructures. This study investigates the internal flow features around circular bridge piers by Particle Image Velocimetry applied both in the horizontal and vertical planes and therefore allowing for a quasi-spatial visualization of the velocity field. The temporal evolution of the vertical deflected flow at the pier front and the horseshoe vortex inside the increasing scour hole were explored resulting in the velocity and vorticity profiles. This work, therefore, provides novel insight into the complex and fascinating two-phase flow around circular bridge piers placed in loose sediment and provides an experimental data basis for advanced numerical simulation.     

Perturbations of positive strongly continuous semigroups on AM spaces

We give a definition for positivity on an extrapolation space for positive strongly continuous semigroups. We prove a perturbation result on AM spaces for positive semigroups by positive operators. Finally, we give an example for this kind of perturbations. (© 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Numerical Solution of Large Scale Sparse Matrix Equations in Python

The M.E.S.S. software suite for solving large scale matrix equations and related problems is the successor of the obsolete LyaPack MATLAB® toolbox. The software suite consists of a new MATLAB toolbox and a separate C library C-M.E.S.S. which works independent from MATLAB. Due to the fact that many scientists use Python with NumPy and SciPy for their computations, we want to provide the key algorithms of M.E.S.S. there as well. In this paper, we describe and compare two possible approaches for the implementation, with special focus on their multicore performance. (© 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)