Study of tin dioxide–sodium stannate composite obtained by decomposition of peroxostannate as a potential anode material for lithium-ion batteries

A tin dioxide–sodium stannate composite has been obtained by the thermal treatment of sodium peroxostannate nanoparticles at 500°C in air. X-ray powder diffraction study has revealed that the composite includes crystalline phases of cassiterite SnO₂, sodium stannate Na₂Sn₂O₅, and sodium hexahydroxostannate Na₂Sn(OH)₆. Scanning electron microscopy has shown that material morphology does not change considerably as compared with the initial tin peroxo compound. Electrochemical characteristics have been compared for the anodes of lithium-ion batteries based on tin dioxide–sodium stannate composite and anodes based on a material manufactured by the thermal treatment of graphene oxide–tin dioxide–sodium stannate composite at 500°C in air.     

Ammonium and caesium carbonate peroxosolvates: supramolecular networks formed by hydrogen bonds

Diammonium carbonate hydrogen peroxide monosolvate, 2NH₄⁺·CO₃²⁻·H₂O₂, (I), and dicaesium carbonate hydrogen peroxide trisolvate, 2Cs⁺·CO₃²⁻·3H₂O₂, (II), were crystallized from 98% hydrogen peroxide. In (I), the carbonate anions and peroxide solvent molecules are arranged on twofold axes. The peroxide molecules act as donors in only two hydrogen bonds with carbonate groups, forming chains along the a and c axes. In the structure of (II), there are three independent Cs⁺ ions, two of them residing on twofold axes, as are two of the four peroxide molecules, one of which is disordered. Both structures comprise complicated three‐dimensional hydrogen‐bonded networks.     

Pyrrolo[3,2‐b]pyrroles—From Unprecedented Solvatofluorochromism to Two‐Photon Absorption

A combined experimental and theoretical study of the two‐photon absorption (2PA) properties of a series of quadrupolar molecules possessing a highly electron‐rich heterocyclic core, pyrrolo[3,2‐b]pyrrole, is presented. In agreement with quantum‐chemical calculations, large 2PA cross‐section values, σ_2PA≈10²–10³ GM (1 GM=10⁵⁰ cm⁴ s photon^?1), are observed at wavelengths of 650–700 nm, which correspond to the two‐photon allowed but one‐photon forbidden transitions. The calculations also predict that increased planarity of this molecule through removal of two N‐substituents leads to further increase in the σ_2PA values. Surprisingly, the most quadrupolar pyrrolo[3,2‐b]pyrrole derivative, containing two 4‐nitrophenyl substituents at positions 2 and 5, demonstrates a very strong solvatofluorochromic effect, with a fluorescence quantum yield as high as 0.96 in cyclohexane, whereas the fluorescence vanishes in DMSO.     

Electrochemical nickel-induced fluoroalkylation: synthetic, structural and mechanistic study

Electrocatalytic generation of nickel catalysts in low oxidation states by reduction of nickel complexes with various ligands (2,2'-bipyridine, 2,2':6',2'-terpyridine, (S,S)-2,6-bis(4-phenyl-2-oxazolin-2-yl)-pyridine) in the presence of olefinic substrates and fluoroalkyl halides leads to new organic products derived from addition-dimerization processes. Due to the presence of two stereocenters in the dimerization products two diastereomers were characterized by a variety of analytical techniques including multi-dimensional NMR methods and X-ray single crystal diffraction. The formation of dimers was prevented by the inclusion of the hydrogen atom donor tributyltin hydride. The cyclic voltammetry study of selected nickel complexes along with fluoroalkyl halides demonstrated that Ni(I)L is the active form of the catalyst.     

Forbidden rotational spectra of axially symmetric polar molecules

In this paper we consider the rotational transitions induced by centrifugal distortion in polar or quasipolar symmetric top molecules belonging to the point groups C_n and C_nv (n ≥ 3). It is shown that in this series only the molecules of point groups C₃, C_3v, C₄, and C_4v may possess rotational spectra induced by first-order centrifugal distortion. A general expression is given for the effective dipole moment operator and for its matrix elements. The peak absorption coefficients for some of the strongest ΔK = 3 transitions of the CH₃D molecule have been calculated and compared with the peak absorption coefficients of allowed transitions.     

Radiation postpolymerization in devitrifying matrices: Different polymerization activity of acrylic and methacrylic monomers

Investigation of the effect of the α-CH₃-group on low-temperature postpolymerization in devitrifying matrices leads to the following conclusions. 1. The low-temperature postpolymerization in supercooled alcohol solutions (T_g ～ 102 K) is quite efficient with acrylic monomers. Inactivity of their methacrylic analogues under these conditions is attributed to steric screening of the unpaired electron in the growing radicals. 2. As the temperature is raised and the CH₃-group vibration intensity increases, the screening effect fades. Thus in devitrifying water-alcohol solutions of NaAA and NaMAA, at higher temperatures the postpolymerization is efficient in both cases. Data on copolymerization of NaAA and NaMAA indicate that at ～ 170 K the steric limitations due to the CH₃-group are eliminated. 3. In a glycerine matrix ($\text{T}{}_{\mathrm{g}}\text{? 195 K}$), all the acrylic and methacrylic monomers studied show efficient polymerization over virtually the same temperature range. It is concluded that the a-CH₃-group in methacrylic monomers appreciably affects their polymerization activity only at low temperatures, where steric screening of the growing polymer radical becomes important.     

Benchmark calculations of some molecular properties of O2, CN and other selected small radicals using the ROHF-CCSD(T) method

The capability of the ROHF-CCSD(T) method in obtaining accurate molecular properties in a defined and controlled way is analysed. Electron affinity, polarizability, and hyperpolarizability of the oxygen molecule in its ground state, electron affinity, electric dipole moment of the CN radical, and some other molecules serve as model cases for obtaining the ‘right result for the right reason’. Most calculated CCSD(T) data were extrapolated to the complete basis set (CBS) limit in order to minimize the basis set dependence of results. Some problems, specific to open shell systems include effects due to the spin adaptation, and details in the selection of the reference orbitals and related selection of denominators in non-iterative triples and other subtleties, which can affect the accuracy of the final ROHF-CCSD(T) results, are investigated.     

Diode pumped actively mode-locked Tm:YAlO3 laser

CW acousto-optical mode-locked diode pumped Tm:YAlO₃ laser at 1.936 μm was experimentally studied. Lasing with output power ～100 mW, pulse repetition rate 103.4 MHz and laser pulse durations in the range of 30–200 ps was realized. The problem of laser intensity stabilization is discussed.