Charge carrier mobility,photovoltaic, and electroluminescent properties of anthracene‐based conjugated polymers bearing randomly distributed side chains

This article reports on the synthesis, characterization, and properties of various anthracene‐containing poly (p‐phenylene‐ethynylene)‐alt‐poly(p‐phenylene‐vinylene) (PPE‐PPV) polymers (AnE‐PVs) bearing statistical distributions of various side chains. Primarily, the ratio of linear octyloxy and branched 2‐ethylhexyloxy side chains at the poly(p‐phenylene vinylene) (PPV) parts was varied, leading to the polymers stat, stat1, and stat2. Furthermore, polymers also containing asymmetric substituted PPV and poly(p‐phenylene ethynylene) units (bearing methoxy and 2‐ethylhexyloxy side chains) were prepared yielding stat3, stat4, and stat5. These materials exhibit a broad variation in their photovoltaic properties. It is once more shown that side chains and their distribution can crucially affect the photovoltaic device performance. The introduction of units with asymmetric substitution into these systems seems to be harmful for their utilization in photovoltaic applications. Organic field‐effect transistors were fabricated to investigate hole mobilities in these new materials. Large variance was observed, falling in the range of almost two orders of magnitude, indicating rather different π–π stacking behavior of the polymer backbones owing to side‐chain modifications. Moreover, a selection of the new polymeric systems was investigated regarding their potential for light‐emitting diode (LED) applications. Polymer LEDs using the polymers AnE‐PVstat, ‐stat3, ‐stat4, and ‐stat5, as the active layer showed turn‐on voltage of ～2 V and exhibited red light emission. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

A novel polymerization approach via thiol‐yne addition

The ability of thiyl radicals to add to terminal unsaturations in an efficient way made them considered being one of the click reactions. Recently, thiol‐yne addition reactions have been used extensively for the synthesis of crosslinked networks and dendrimers and postpolymerization functionalization protocols. Herein, we report a novel step‐growth type reaction for highly functional linear polymers using a monoalkyne and dithiol compound. First, we investigated the model reaction between 1‐octyne and 1‐octanethiol as well as 1,4‐butanedithiol compounds, which were initiated via self‐, thermal‐, and UV‐initiation; the UV‐initiation was found to be the most efficient method and completed within 2‐h reaction time. The same conditions were applied for the polymerization of four different functional alkynes bearing different functional groups with two dithiol compounds. All polymerizations resulted in highly functional linear polymers with number averaged molecular weights ranging from 5 to 30 kDa, except for propargylic acid and its methyl ester, where only oligomers formed. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

SPE and determination by FAAS of heavy metals using a new synthesized polymer resin in various water and dried vegetables samples

Firstly, poly[phenyl thiadiazole methacrylamide-co-divinylbenzene-co-2-acrylamido-2-methylpropane sulfonic acid] (PTMAAm-co-DVB-co-AMPS), a new polymer resin was synthesized. This polymer resin was characterized by elemental analyzer, X-ray diffractometer, scanning electron microscope (SEM) and IR spectrometer. The glass column packed with the synthesized polymer resin was used for solid phase extraction (SPE). At the same time, the analytes were separated and preconcentrated from various water, dried vegetables samples and standard reference material (CRM) with SPE and determined by flame atomic absorption spectrometer (FAAS). The experimental conditions of this method such as pH, flow rates of sample, flow rates of eluent, type / concentration / volume of eluent, sample volume and matrix ions were examined. The limits of detection (µg L^?1) were calculated (3s) 0.9 for Mn(II), 1.4 for Cd(II), Co(II) and Zn(II), 1.5 for Cr(III), 2.2. for Cu(II), 1.9 for Pb(II),1.5 for Ni(II) and 1.9 for Fe(III) (n = 21). The low relative standard deviation, ≤ 2% (n = 11) and preconcentration factor as 75 for analytes were obtained.     

New chiral ruthenium(II)–phosphinite complexes containing a ferrocenyl group in enantioselective transfer hydrogenations of aromatic ketones

A new and versatile class of unsymmetrical ferrocenyl-phosphinite ligands possessing a stereogenic center has been prepared from commercially available, inexpensive aminoacids such as, d-, l-phenylglycine and d-, l-phenylalanine, through a concise synthetic procedure. These ligands are not very sensitive to air and moisture, and display good enantioselectivities in the ruthenium-catalyzed asymmetric transfer hydrogenation of acetophenone derivatives, in which up to 91% ee was obtained. A comparison of the catalytic properties of amino alcohols and other analogues based on a ferrocenyl backbone is also discussed briefly. The structures of these ligands and their corresponding complexes have been elucidated by a combination of multinuclear NMR spectroscopy, IR spectroscopy, and elemental analysis.     

A Frustrated Phosphane–Borane Lewis Pair and Hydrogen: A Kinetics Study

The energy profile of a frustrated Lewis pair (FLP) dihydrogen splitting system was determined by a combined experimental kinetic and DFT study. A trimethylene‐bridged phosphane–borane FLP was converted into its endothermic H₂‐cleavage product by sequential H⁺/H^? addition. The system could be handled at low temperature, and the kinetics of the H₂ elimination were determined to give a rate constant of k_HH,exp(299 K)=(2.87±0.1)×10^?4 s^?1 in solution. The primary kinetic isotope effects were determined; for example, (k_HH/k_DD)_exp=3.19. The system was accurately analyzed by DFT calculations.     

Intermediate behavior of Kerr tails

The numerical investigation of wave propagation in the asymptotic domain of Kerr spacetime has only recently been possible thanks to the construction of suitable hyperboloidal coordinates. The asymptotics revealed an apparent puzzle in the decay rates of scalar fields: the late-time rates seemed to depend on whether finite distance observers are in the strong field domain or far away from the rotating black hole, an apparent phenomenon dubbed ‘splitting.’ We discuss far-field ‘splitting’ in the full field and near-horizon ‘splitting’ in certain projected modes using horizon-penetrating, hyperboloidal coordinates. For either case we propose an explanation to the cause of the ‘splitting’ behavior, and we determine uniquely decay rates that previous studies found to be ambiguous or immeasurable. The far-field ‘splitting’ is explained by competition between projected modes. The near-horizon ‘splitting’ is due to excitation of lower multipole modes that back excite the multipole mode for which ‘splitting’ is observed. In both cases ‘splitting’ is an intermediate effect, such that asymptotically in time strong field rates are valid at all finite distances. At any finite time, however, there are three domains with different decay rates whose boundaries move outwards during evolution. We then propose a formula for the decay rate of tails that takes into account the inter-mode excitation effect that we study.