Revealing Phosphorus Nitrides up to the Megabar Regime: Synthesis of α′-P3N5, δ-P3N5 and PN2

Non-metal nitrides are an exciting field of chemistry, featuring a significant number of compounds that can possess outstanding material properties. These properties mainly rely on maximizing the number of strong covalent bonds, with crosslinked XN₆ octahedra frameworks being particularly attractive. In this study, the phosphorus–nitrogen system was studied up to 137 GPa in laser-heated diamond anvil cells, and three previously unobserved phases were synthesized and characterized by single-crystal X-ray diffraction, Raman spectroscopy measurements and density functional theory calculations. δ-P₃N₅ and PN₂ were found to form at 72 and 134 GPa, respectively, and both feature dense 3D networks of the so far elusive PN₆ units. The two compounds are ultra-incompressible, having a bulk modulus of K₀=322 GPa for δ-P₃N₅ and 339 GPa for PN₂. Upon decompression below 7 GPa, δ-P₃N₅ undergoes a transformation into a novel α′-P₃N₅ solid, stable at ambient conditions, that has a unique structure type based on PN₄ tetrahedra. The formation of α′-P₃N₅ underlines that a phase space otherwise inaccessible can be explored through materials formed under high pressure.     

Electron Transport in Configurational Model of Ferromagnetic Fulleride with Triple Orbital Degeneracy

Abstract

Phenomenon of ferromagnetic ordering was for a long time associated exclusively with transition metal and rare-earth compounds. Nowadays this view is challenged by growing evidence that in molecular carbon-based systems the ferromagnetic alignment of spins can be observed as well. We have developed a microscopical model of a fulleride electronic subsystem taking into account triple orbital degeneracy of energy states within the configurational-operator approach. Using the Green function method the energy spectrum of the model has been calculated. Conditions for the ferromagnetic state stabilization have been determined. Static electrical conductivity and effective masses of current carriers in the system with orbitally degenerated energy band have been obtained. In the ground state and for low temperatures at different forms of unperturbed density of electronic states the concentration dependences of transport characteristics for less-then-half-filled lower quasiparticle subband have been calculated.     

Microwave-Assisted Conversion of Carbohydrates

Catalytic conversion of carbohydrates into value-added products and platform chemicals became a trend in recent years. Microwave activation used in the processes of carbohydrate conversion coupled with the proper choice of catalysts makes it possible to enhance dramatically the efficiency and sometimes the selectivity of catalysts. This mini-review presents a brief literature survey related to state-of-the-art methods developed recently by the world research community to solve the problem of rational conversion of carbohydrates, mostly produced from natural resources and wastes (forestry and agriculture wastes) including production of hydrogen, synthesis gas, furanics, and alcohols. The focus is made on microwave technologies used for processing carbohydrates. Of particular interest is the use of heterogeneous catalysts and hybrid materials in processing carbohydrates.     

Facile Synthesis of Bis(crown ether)benzils: Prospective Building Blocks for Metal Ion Sensors

A new facile synthetic route to benzils containing fragments of 12-crown-4, 15-crown-5, and 18-crown-6 by oxidation of corresponding stilbenes was developed. The first representative of a new family of fluorescent sensors was obtained by reaction of bis(15-crown-5)benzil with o-phenylenediamine. The latter exhibits great fluorescence enhancement upon association with K⁺ and Rb⁺ compared to Na⁺ and Cs⁺.     

Structural trends of 29Si–1H spin–spin coupling constants across double bond

The calculations of geminal and vicinal ²⁹Si–¹H spin–spin coupling constants across double bond in 15 alkenylmethylsilanes and alkenylchlorosilanes were carried out at the second‐order polarization propagator approach level in a good agreement with experiment. Two structural trends, namely, (i) the geometry of the coupling pathway and (ii) the effect of the electrowithdrawing substituent, have been interpreted in terms of the natural J‐coupling analysis within the framework of the natural bond orbital approach. Thus, the marked difference between cisoidal and transoidal ²⁹Si–¹H spin–spin coupling constants across double bond was accounted for the delocalization contributions including bonding and antibonding Si–C and C–H orbitals, whereas the chlorine effect was explained in terms of the steric contributions including bonding Si–Cl orbitals. Copyright © 2012 John Wiley & Sons, Ltd.     

Normal halogen dependence of 13C NMR chemical shifts of halogenomethanes revisited at the four‐component relativistic level

The ‘Normal Halogen Dependence’ of ¹³C NMR chemical shifts in the series of halogenomethanes is revisited at the four‐component relativistic level. Calculations of ¹³C NMR chemical shifts of 70 halogenomethanes have been carried out at the density functional theory (DFT) and MP2 levels with taking into account relativistic effects using the four‐component relativistic theory of Dirac‐Coulomb within the different computational methods (4RPA, 4OPW91) and hybrid computational schemes (MP2 + 4RPA, MP2 + 4OPW91). The most efficient computational protocols are derived for practical purposes. Relativistic shielding effect reaches as much as several hundreds of ppm for heavy halogenomethanes, and to account for this effect in comparison with experiment at the qualitative level, relativistic Dyall's basis sets of triple‐zeta quality or higher are to be used within the framework of the four‐component relativistic theory taking into account solvent effects. Relativistic geometrical optimization (as compared with the non‐relativistic level) is essential for the molecules containing at least two iodines at one carbon atom. Copyright © 2016 John Wiley & Sons, Ltd.     

Open‐chain unsaturated selanyl sulfides: stereochemical structure and stereochemical behavior of their 77Se–1H spin–spin coupling constants

Stereochemical structure of nine Z‐2‐(vinylsulfanyl)ethenylselanyl organyl sulfides has been investigated by means of experimental measurements and second‐order polarization propagator approach calculations of their ¹H–¹H, ¹³C–¹H, and ⁷⁷Se–¹H spin–spin coupling constants together with a theoretical conformational analysis performed at the MP2/6‐311G** level. All nine compounds were shown to adopt the preferable skewed s‐cis conformation of their terminal vinylsulfanyl group, whereas the favorable rotational conformations with respect to the internal rotations around the C–S and C–Se bonds of the internal ethenyl group are both skewed s‐trans. Stereochemical trends of ⁷⁷Se–¹H spin–spin coupling constants originating in the geometry of their coupling pathways and the selenium lone pair effect were rationalized in terms of the natural J‐coupling analysis within the framework of the natural bond orbital approach. Copyright © 2012 John Wiley & Sons, Ltd.     

Stereochemical behavior of 2 J(Se,H) and 3 J(Se,H) spin‐spin coupling constants across sp3 carbons: a theoretical scrutiny

A theoretical study of geminal and vicinal ⁷⁷Se‐¹ H coupling constants in the benchmark dimethyl and diethyl selenides has been performed at the SOPPA level followed by the NJC analysis within the NBO approach to reveal their stereochemical behavior in respect with the three main structural factors, namely, (i) the dihedral angle dependences, (ii) the bond angle dependences and (iii) the lone pair effects. It has been demonstrated that both geminal and vicinal couplings provide a unique stereospecificity in respect with the orientational lone pair effect together with the geometry of a coupling pathway, which is of prime importance for the stereochemical studies of organoselenium compounds. Copyright © 2012 John Wiley & Sons, Ltd.