Generation of fullerenyl radicals and chemiluminescence in the (C<Subscript>60</Subscript>—R<Subscript>3</Subscript>Al)—O<Subscript>2</Subscript> system

Fullerenyl radicals (FR) RC₆₀ ^· and chemiluminescence (CL) are generated in the presence of O₂ in C₆₀—R₃Al (R = Et, Buⁱ) solutions in toluene (T = 298 K). The FR are formed due to the addition of the R^· radical, which is an intermediate of R₃Al autooxidation, to C₆₀. Mass spectroscopy and HPLC were used to identify Et_nC₆₀H_m (n, m = 1–6), Et_pC₆₀ (p = 2–6), and dimer EtC₆₀C₆₀Et as stable products of FR transformations. As found by ESR, the EtC₆₀ ^· radical (g = 2.0037) is also generated by photolysis of solutions obtained after interaction in the (C₆₀— R₃Al)—O₂ system. In the presence of dioxygen, the FR is not oxidized but yields complexes with O₂, which appear as broadening of the ESR signals. Chemiluminescence arising in the (C₆₀—R₃Al)—O₂ system is much brighter (I _max = 1.86·10⁸ photon s⁻¹ mL⁻¹) than the known background CL (I _max = 6.0·10⁶ photon s⁻¹ mL⁻¹) for the autooxidation of R₃Al and is localized in a longer-wavelength spectral region (λ_max = 617 and 664 nm). This CL is generated as a result of energy transfer from the primary emitter ³CH₃CHO* to the products of FR transformation: R_nC₆₀H_m, R_pC₆₀, and EtC₆₀C₆₀Et. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 205–213, February, 2007.     

Homodimerization of spiro{bicyclo[2.2.1]Hepta-2,5-Diene-7,1′-cyclopropane}, catalyzed by group VIII transition metal complexes

Conclusions The homodimerization of spiro{bicyclo[2.2.1]hepta-2,5-diene-7,1-cyclopropane} (I) has been investigated in the presence of Ni-, Fe-, Co-, Rh-, and Ir-based metal complex catalysts. Depending on the nature of the metal and its ligand environment cyclodimerization of (I) can take place via [2+2]-, [2+2+2]-, and [4+4]-cycloaddition schemes, to give high yields of hepta-, octa-, and nonacyclic strained hydrocarbons.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 11, pp. 2592–2599, November, 1988.     

13C NMR Spectra of polycyclic compounds: stereochemistry of spiro(bicyclo[2.2.1]hepta-2,5-diene-7,1′-cyclopropane) dimers

The structures of the dimerization products of spiro(bicyclo[2.2.1]hepta-2,5-diene-7,1-cyclopropane) have been solved using¹³C NMR spectroscopy and their stereochemical assignments made. The methylene carbon atom signals for the spirocyclopropane fragment can be used as diagnostic signals in making the stereochemical assignments.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 3, pp. 559–564, March, 1990.     

Oleophobic properties of the step-and-terrace sapphire surface

Crystallography Reports - Sapphire is widely used in production of optical windows for various devices due to its mechanical and optical properties. However, during operation the surface can be...     

7α-alkylation, 7,7-bisalkylation,and reduction of the 20-oxo group of poststerone in reactions with alkyl halides in lithium–ammonia solution

Reactions of poststerone with methyl iodide, allyl bromide, and propargyl bromide in lithium–ammonia solution resulted in its completely stereoselective 7α-alkylation accompanied by reduction of the 20-oxo group with formation of equimolar amounts of 20R- and 20S-hydroxy derivatives. The reaction of poststerone with excess allyl bromide afforded 7,7-bis-allyl 20R- and 20S-alcohols at a ratio of 3: 1. The reduction of the 20-oxo group in the alkylation of poststerone with excess propargyl bromide led to the formation of an equimolar mixture of Δ⁸⁽¹⁴⁾- and Δ⁸⁽⁹⁾-isomers with exclusive S configuration of C²⁰.     

Catalytic epitaxy of ZnO whiskers via the vapor–crystal mechanism

A model of oriented growth of (0001) ZnO whiskers on sapphire substrates via the vapor–crystal mechanism using the catalytic properties of gold islands is proposed. The morphological transition from the primary pyramidal ZnO structures to hexagonal ZnO whiskers is described in terms of the minimization of the free energy density of three-dimensional heteroepitaxial islands.     

Characterization of single-crystal sapphire substrates by X-ray methods and atomic force microscopy

The possibility of characterizing a number of practically important parameters of sapphire substrates by X-ray methods is substantiated. These parameters include wafer bending, traces of an incompletely removed damaged layer that formed as a result of mechanical treatment (scratches and marks), surface roughness, damaged layer thickness, and the specific features of the substrate real structure. The features of the real structure of single-crystal sapphire substrates were investigated by nondestructive methods of double-crystal X-ray diffraction and plane-wave X-ray topography. The surface relief of the substrates was investigated by atomic force microscopy and X-ray scattering. The use of supplementing analytical methods yields the most complete information about the structural inhomogeneities and state of crystal surface, which is extremely important for optimizing the technology of substrate preparation for epitaxy.     

Ordered gold nanostructures on sapphire surfaces: Fabrication and optical investigations

The possibilities of obtaining ordered gold nanoarrays on sapphire surfaces with oriented nanorelief are demonstrated. The structures are morphologically described using atomic force microscopy data. A study of the angular dependence of the reflectivity in the visible range of electromagnetic waves has revealed some features which are likely to indicate surface plasmon-polariton excitation at the air-gold interface under exposure to p-polarized radiation. The experimental results are found to be in good agreement with the theoretical calculations.     

Effect of the Morphology of an Ensemble of ZnO Microrods on the Optical and Luminescence Properties

JETP Letters - From measurements of the oscillatory magnetoresistance in weak perpendicular magnetic fields, we found that the quantum oscillations in two-dimensional electron systems in Si-MOS...     

X-Ray Luminescence of ZnO Tetrapods Grown in the Presence of Copper and Gold Admixtures in Initial Charge

Optics and Spectroscopy - We investigated the morphology and luminescent properties of ZnO tetrapod powders with copper and gold admixtures, obtained by carbothermal pyrolysis. A broad band in the...