Nature of catalytic effect of Ni(O)- and BF3OEt2-based systems in propene dimerization

¹H NMR, EPR and IR spectroscopic studies of the products of the interaction between components of the Ni[PPh₃]₄+EtOH+BF₃.OEt₂ and Ni(PPh₃)₄+BF₃OEt₂ systems suggest the formation of two types of complexes [HNi(PP₃)₃L]⁺[BF₃OEt]^– and [Ni(PPh₃)₃L]⁺BF ₄ ^– , which are catalytically active in propene dimerization.

---

¹H, , - Ni(PPh₃)₄+ EtOH+BF₃OEt₂ Ni(PPh₃)₄+BF₃·OEt₂ [HNi (PPh₃)₃L]⁺ [BF₃OEt]^– [Ni (PPh₃)L₂]⁺BF ₄ ^– .

     

Exploration of the Crystal Structure and Thermal and Spectroscopic Properties of Monoclinic Praseodymium Sulfate Pr2(SO4)3

Praseodymium sulfate was obtained by the precipitation method and the crystal structure was determined by Rietveld analysis. Pr₂(SO₄)₃ is crystallized in the monoclinic structure, space group C2/c, with cell parameters a = 21.6052 (4), b = 6.7237 (1) and c = 6.9777 (1) Å, β = 107.9148 (7)°, Z = 4, V = 964.48 (3) ų (T = 150 °C). The thermal expansion of Pr₂(SO₄)₃ is strongly anisotropic. As was obtained by XRD measurements, all cell parameters are increased on heating. However, due to a strong increase of the monoclinic angle β, there is a direction of negative thermal expansion. In the argon atmosphere, Pr₂(SO₄)₃ is stable in the temperature range of T = 30–870 °C. The kinetics of the thermal decomposition process of praseodymium sulfate octahydrate Pr₂(SO₄)₃·8H₂O was studied as well. The vibrational properties of Pr₂(SO₄)₃ were examined by Raman and Fourier-transform infrared absorption spectroscopy methods. The band gap structure of Pr₂(SO₄)₃ was evaluated by ab initio calculations, and it was found that the valence band top is dominated by the p electrons of oxygen ions, while the conduction band bottom is formed by the d electrons of Pr³⁺ ions. The exact position of ZPL is determined via PL and PLE spectra at 77 K to be at 481 nm, and that enabled a correct assignment of luminescent bands. The maximum luminescent band in Pr₂(SO₄)₃ belongs to the ³P₀ → ³F₂ transition at 640 nm.     

One-Dimensional Particle Processes with Acceleration/Braking Asymmetry

The slow-to-start mechanism is known to play an important role in the particular shape of the Fundamental Diagram of traffic and to be associated to hysteresis effects of traffic flow. We study this question in the context of exclusion and queueing processes, by including an asymmetry between deceleration and acceleration in the formulation of these processes. For exclusions processes, this corresponds to a multi-class process with transition asymmetry between different speed levels, while for queueing processes we consider non-reversible stochastic dependency of the service rate w.r.t. the number of clients. The relationship between these 2 families of models is analyzed on the ring geometry, along with their steady state properties. Spatial condensation phenomena and metastability are observed, depending on the level of the aforementioned asymmetry. In addition, we provide a large deviation formulation of the fundamental diagram which includes the level of fluctuations, in the canonical ensemble when the stationary state is expressed as a product form of such generalized queues.     

Cyclometallated 1,2,3-triazol-5-ylidene iridium(III) complexes: synthesis,structure, and photoluminescence properties

1. Download high-res image (67KB)
2. Download full-size image

     

Tuning the morphology and magnetic properties of single-domain SrFe8Al4O19 particles prepared by a citrate auto-combustion method

1. Download : Download high-res image (184KB)
2. Download : Download full-size image

     

Model‐independent structure and resonant X‐ray spectra of intermediate smectic phases

It is shown that the orientational structure of intermediate smectic phases can be determined using the symmetry properties of the general free energy with arbitrary orientational coupling between smectic layers, without addressing a particular model. The structure of three‐ and four‐layer intermediate phases, obtained in this way, corresponds to experimental data. The same method enables one to predict the structure of intermediate phases with periodicity of five and six layers, which have not been observed experimentally so far. The resonant X‐ray spectra of the five‐ and six‐layer intermediate phases with predicted structure have also been calculated. These spectra are characterized by a number of features which enable one to distinguish five‐layer and six‐layer intermediate phases from phases with smaller periods.     

Ferroelectric liquid crystal composites based on the porous stretched polyethylene films

Electro-optically active polymer–liquid crystal composites based on ferroelectric liquid crystals and stretched porous polyethylene films were developed. The alignment of ferroelectric liquid crystals incorporated into the porous polyethylene films with average porous diameter of around 200 nm was observed and studied. It was shown experimentally that these samples containing ferroelectric liquid crystals are flexible electro-optical films exhibiting a saturation electric field near 2·10⁷ Vm^?1 and a response time of about 30 μs under the action of the saturation field. A simple theoretical model of ferroelectric liquid crystal molecules' complete reorientation in electric fields inside pores of the films has been proposed and confirmed experimentally.     

Synthesis of polyampholyte microgels from colloidal salts of pectinic acid and their application as pH-responsive emulsifiers

A novel method for obtaining cross-linked microgels of apple pectin has been introduced. This method is based on the Ugi four-component condensation in colloidal suspensions of pectinic acid and amines. Using various processing parameters (the polysaccharide concentration, the type and density of crosslink, and the optimal pH range), particles with controlled colloidal properties have been obtained. Lightly cross-linked polysaccharide chains acquire anionic character due to deprotonation of the carboxyl groups at pH?9–10. Increasing the degree of cross-linking leads to a polyampholyte microgel, which can be protonated in acidic medium or deprotonated in basic medium. Polyampholyte microgels derived from apple pectin have proved to be an effective Pickering emulsifier at low concentrations and pH?2–3, forming stable oil-in-water emulsions. These Pickering emulsions exhibited pH-responsive behavior: raising the solution pH to 10 resulted in immediate demulsification due to the destabilization of microgel network at the oil–water interface.