Synthesis and capsule formation of upper rim substituted tetra-acrylamido calix[4]arenes

Upper rim substituted tetraiodo calix[4]arenes are coupled to a variety of acrylamides using the palladium catalysed Heck reaction. Tetra-acrylamido upper rim substituted calix[4]arenes are obtained in good yields with exceptionally high stereoselectivity, to produce the all-trans isomers. Tetra-acrylamido calix[4]arenes derived from secondary acrylamides are shown to dimerise via eight hydrogen bonds to form dimeric capsules, which are able to include small organic molecules.     

Mass spectra of alditol trifluoroacetates

The trifluoroacetyl derivatives of alditols are convenient compounds for mass spectrometric investigation as they are easily obtainable and highly volatile. They show simple fragmentation patterns with intensive peaks in the high mass range. Trifluoroacetates of alditols may be used for detection and location of deoxy groups in the molecule.     

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.     

REACTION OF LITHIUM DERIVATIVE OF DIETHYL PHENYLMETHANE-PHOSPHONATE WITH KETONES

Abstract

The reaction of the lithium derivative of diethyl ester of phenylmethanephosphonic acid (1-Li) with alkanones, cycloalkanones, alkylaryl and diarylketones 2s-b is studied at -70°C in THF. The corresponding adducts-diethyl esters of l-phenyl-2,2-dialkyl(phenyl)-2-hydroxyethanephosphonic acids 3s-h are isolated, their yields being usually higher at short reaction time. The olefination of 3-Li as well as of 3 (both by thermolysis or in acidic media) proceeds in low degree, while in the case of 3-Na the yields of alkenes 4 are good. The relative configurations of 3b. 31 and 3g are determined by IR and NMR-spectra, as well as by their stereospecific olefination. “Threo”-stereoselectivity of the addition stage of the reaction of 1-Li with 2b, 21 and 2g is observed, the “threo”/“erythro” ratio remaining independent on the reaction time.     

First-principles prediction and partial characterization of the vibrational states of water up to dissociation

A new, accurate, global, mass-independent, first-principles potential energy surface (PES) is presented for the ground electronic state of the water molecule. The PES is based on 2200 energy points computed at the all-electron aug-cc-pCV6Z IC-MRCI(8,2) level of electronic structure theory and includes the relativistic one-electron mass-velocity and Darwin corrections. For H₂¹⁶O, the PES has a dissociation energy of D₀ = 41 109 cm⁻¹ and supports 1150 vibrational energy levels up to 41 083 cm⁻¹. The deviation between the computed and the experimentally measured energy levels is below 15 cm⁻¹ for all the states with energies less than 39 000 cm⁻¹. Characterization of approximate vibrational quantum numbers is performed using several techniques: energy decomposition, wave function plots, normal mode distribution, expectation values of the squares of internal coordinates, and perturbing the bending part of the PES. Vibrational normal mode labels, though often not physically meaningful, have been assigned to all the states below 26 500 cm⁻¹ and to many more above it, including some highly excited stretching states all the way to dissociation. Issues to do with calculating vibrational band intensities for the higher-lying states are discussed.     

Structure of trans-1,4-polybutadiene synthesized with a new catalyst system

Abstract

The structure, phase composition, and temperature behavior of two trans-1,4-polybutadienes (TPBs) were studied by means of x-ray scattering and differential scanning calorimetry (DSC) techniques. The two samples examined were (1) PB synthesized using an immobilized titanium-magnesium catalyst and (2) a random copolymer based on PB prepared with a homogeneous vanadium-containing catalyst used as a reference material. It was found that the nascent structure of the first PB involves three phases: crystalline, mesomorphic (low-temperature form), and amorphous. In the vicinity of 65°C, a first-order phase transition occurs. The system becomes biphasic and contains the high-temperature form of the mesophase, as well as the amorphous phase, component. Above 165°C, the polymer melts to form a single-phase isotropic melt with a structure typical of liquids. The lateral dimension of crystallites reversibly changes at the crystal-mesophase transition. It is suggested that during annealing of the mesophase formed by cooling of the isotropic melt, the chains acquire an extended conformation. Loss of regularity of the structure of macromolecules of TPB causes a reduction of phase transition temperatures, an increase of the imperfection of the crystalline phase, and a contraction of the temperature range of existence of the mesophase.     

Electrical Current in Sinai Billiards Under General Small Forces

The Lorentz gas of $\mathbb{Z}^{2}$ -periodic scatterers (or the so called Sinai billiards) can be used to model motion of electrons on a metal. We investigate the linear response for the system under various external forces (during both the flight and the collision). We give some characterizations under which the forced system is time-reversible, and derive an estimate of the electrical current generated by the forced system. Moreover, applying Pesin entropy formula and Young dimension formula, we get several characterizations of the non-equilibrium steady state of the forced system.     

Shallow Donors and Deep-Level Color Centers in Bulk AlN Crystals: EPR, ENDOR, ODMR and Optical Studies

The results of studies of shallow donors and deep-level color centers in bulk AlN crystals are presented. Two shallow donors (presumably oxygen located on the nitrogen site and carbon located on the aluminum site) are suggested to exhibit the DX-relaxation. Third shallow donor (presumably silicon on the Al site) shows the shallow donor behavior up to the room temperature and can be observed without light excitation at temperatures above 200 K. The values of the Bohr radius of the shallow donors are estimated. The structure of deep-level color centers (neutral nitrogen vacancy V _N) in bulk AlN crystals is determined and analyzed by electron paramagnetic resonance, electron-nuclear double resonance, optical absorption and thermoluminescence induced by X-ray irradiation. Spin-dependent recombination processes in AlN crystals are studied by means of optically detected magnetic resonance.     

Interaction of Au nanowires with impurities

We report the results of our first-principles studies of the interaction between an infinite monoatomic gold nanowire and a carbon-monoxide molecule. We show that the gold monoatomic nanowire is capable of absorbing the CO molecule at the distances of about 1.8 ? and forms a bond with the carbon atom. Further, we find that dissociation of the CO molecule as the source of gold nanowire contamination with carbon, which is widely discussed in literature as the possible reason for the striking stability of gold nanowires under stretching, is thermodynamically unfavored.     

The Ising version of the t–J model

The t–J model is analysed in the limit of strong anisotropy, where the transverse components of electron spin are neglected. We propose a slave-particle-type approach that is valid, in contradiction to many of the standard approaches, in the low-doping regime and becomes exact for a half-filled system. We describe an effective method that allows to numerically study the system with the no-double-occupancy constraint rigorously taken into account at each lattice site. Then, we use this approach to demonstrate the destruction of the antiferromagnetic order by increasing the doping and formation of Nagaoka polarons in the strong interaction regime.