Magnetooptics in Gold and Silver NanoSizes Low-Dimensional Objects

The spectra of optical absorption and of magnetic circular dichroism (MCD) have been measured in the 350–1150 nm wavelength range for a set of colloidal solutions containing Au and Ag nanoparticles. The average size of Au nanoparticles was 6 nm and having thiolate coatings with different degrees of chirality. (The average size of Ag nanoparticles was 14 nm and having citrate coatings) The form of absorption and MCD spectra suggests the dipole character of interband transitions involving the 5d–6(sp) for Au orbitals and 4d–5(sp) for Ag orbitals. The absence (within the experimental error) of the MCD spectra dependence on the coating type rules out the hypothesis on the orbital nature of the observed magnetism. We argue that the spin polarization plays the dominant role in the magnetism both for Au and Ag nanoparticles. When you are citing the document, use the following link http://essuir.sumdu.edu.ua/handle/123456789/3534

Near Ambient Pressure XPS and MS Study of CO Oxidation over Model Pd Au HOPG Catalysts The Effect of the Metal Ratio

In this study, the dependence of the catalytic activity of highly oriented pyrolytic graphite HOPG supported bimetallic Pd Au catalysts towards the CO oxidation based on the Pd Au atomic ratio was investigated. The activities of two model catalysts differing from each other in the initial Pd Au atomic ratios appeared as distinctly different in terms of their ignition temperatures. More specifically, the PdAu 2 sample with a lower Pd Au surface ratio 0.75 was already active at temperatures less than 150 C, while the PdAu 1 sample with a higher Pd Au surface ratio 1.0 became active only at temperatures above 200 C. NAP XPS revealed that the exposure of the catalysts to a reaction mixture at RT induces the palladium surface segregation accompanied by an enrichment of the near surface regions of the two component Pd Au alloy nanoparticles with Pd due to adsorption of CO on palladium atoms. The segregation extent depends on the initial Pd Au surface ratio. The difference in activity between these two catalysts is determined by the presence or higher concentration of specific active Pd sites on the surface of bimetallic particles, i.e., by the ensemble effect. Upon cooling the sample down to room temperature, the reverse redistribution of the atomic composition within near surface regions occurs, which switches the catalyst back into inactive state. This observation strongly suggests that the optimum active sites emerge under reaction conditions exclusively, involving both high temperature and a reactive atmospher

SRPES and STM data for the model bimetallic Pd In HOPG catalysts Effects of mild post synthesis oxidative treatments

Post synthesis treatment of bimetallic catalysts in different gas phases resulting in the adsorption induced segregation is among promising approaches to enhance their activity not compromising selectivity towards a number of low temperature reactions. Our recently published paper M.A. Panafidin, A.V. Bukhtiyarov, I.P. Prosvirin, I.A. Chetyrin, A.Yu. Klyushin, A. Knop Gericke, N.S. Smirnova, P.V. Markov, I.S. Mashkovsky, Y.V. Zubavichus, A.Yu. Stakheev, V.I. Bukhtiyarov, A mild post synthesis oxidative treatment of Pd In HOPG bimetallic catalysts as a tool of their surface structure fine tuning. Appl. Surf. Sci. reports on Pd In intermetallic formation regularities and their evolution after storage in air as well as during treatment in oxygen at submillibar pressures. The current paper gives an extended representation of experimental ex situ in situ synchrotron based photoelectron spectroscopy SRPES and scanning tunnelling microscopy STM data used to derive scientific conclusions in the paper quoted abov

High-throughput small-molecule crystallography at the ‘Belok’ beamline of the Kurchatov synchrotron radiation source: Transition metal complexes with azomethine ligands as a case study

This paper concisely describes capabilities of the ‘Belok’ beamline at the Kurchatov synchrotron radiation source, related to high-throughput small-molecule X-ray crystallography. As case examples, a series of four novel transition metal complexes with azomethine ligands were selected. The complexes demonstrate somewhat unexpected changes in the coordination geometry and nuclearity in response to the introduction of substituents in the ligand’s periphery. © 2017 by the authors

Crystal structure of bis{1-phenyl-3-methyl-4-[(quinolin-3-yl)iminomethyl-κN]-1H-pyrazol-5-olato-κO}zinc methanol 2.5-solvate from synchrotron X-ray diffraction

The title compound, [Zn(C20H15N4O)2]·2.5CH3OH, I, was synthesized via the reaction of zinc acetate with the respective ligand and isolated as a methanol solvate, i.e., as I·2.5CH3OH. The crystal structure is triclinic (space group P1), with two complex molecules (A and B) and five methanol solvent molecules in the asymmetric unit. One of the five methanol solvent molecules is disordered over two sets of sites, with an occupancy ratio of 0.75:0.25. Molecules A and B are conformers and distinguished by the conformations of the bidentate 1-phenyl-3-methyl-4-[(quinolin-3-yl)iminomethyl]-1H-pyrazol-5-olate ligands. In both molecules, the zinc cations have distorted tetrahedral coordination spheres, binding the monoanionic ligands through the pyrazololate O and imine N atoms. The two ligands adopt slightly different conformations in terms of the orientation of the terminal phenyl and quinoline substituents with respect to the central pyrazololate moiety. The molecular geometries of A and B are supported by intramolecular C - H⋯O and C - H⋯N hydrogen bonds. In the crystal of I, molecules form dimers both by secondary intermolecular Zn⋯O [3.140 (2)-3.553 (3) Å] and π-π stacking interactions. The dimers are linked by intermolecular hydrogen bonds through the solvent methanol molecules into a three-dimensional network. © Burlov et al. 2017

Hydride transfer reactions of 5-(2-alkohybenzylidene) barbituric acids: Synthesis of 2,4,6-trioxoperhydropyrimidine-5-spiro-3′-chromanes

The thermal cyclization of 5-(2-phenoxymethylphenyl-methylene)barbituric acid and its derivatives affords 2,4,6-trioxoperhydropyrimidine-5-spiro-3′-chromanes. The reactions require no catalysts and proceed at temperatures from 118 to 240 °C depending on the substrate activity. These cyclization reactions are analogous to T-reactions of tertiary amines involving the hydride transfer. © 2016 Elsevier Lt

Crystal structures of the two epimers from the unusual thermal C6-epimerization of 5-oxo-1,2,3,5,5a,6,7,9b-octahydro-7,9a-epoxypyrrolo[2,1-a]isoindole-6-carboxylic acid, 5a(RS),6(SR),7(RS),9a(SR),9b(SR) and 5a(RS),6(RS),7(RS),9a(SR),9b(SR)

The isomeric title compounds, C12H13NO4 (Ia) and C12H13NO4 (IIa), the products of an usual thermal C6-epimerization of 5-oxo-1,2,3,5,5a,6,7,9b-octahydro-7,9a-epoxypyrrolo[2,1-a]isoindole-6-carboxylic acid, represent the two different diastereomers and have very similar molecular geometries. The molecules of both compounds comprise a fused tetracyclic system containing four five-membered rings (pyrrolidine, pyrrolidinone, dihydrofuran and tetrahydrofuran), all of which adopt the usual envelope conformations. The dihedral angle between the basal planes of the pyrrolidine and pyrrolidinone rings are 14.3 (2) and 16.50 (11)°, respectively, for (Ia) and (IIa). The nitrogen atom has a slightly pyramidalized geometry [bond-angle sum = 355.9 and 355.3°, for (Ia) and (IIa)], respectively. In the crystal of (Ia), molecules form zigzag-like hydrogen-bonded chains along [010] through strong O - H⋯O hydrogen bonds and are further linked by weak C - H⋯O hydrogen bonds into complex two-tier layers parallel to (100). Unlike (Ia), the crystal of (IIa) contains centrosymmetric cyclic hydrogen-bonded dimers [graph set R 2 2(14)], formed through strong O - H⋯O hydrogen bonds and are further linked by weak C - H⋯O hydrogen bonds into ribbons extending across [101]

High-throughput small-molecule crystallography at the ‘Belok’ beamline of the Kurchatov synchrotron radiation source: Transition metal complexes with azomethine ligands as a case study

This paper concisely describes capabilities of the ‘Belok’ beamline at the Kurchatov synchrotron radiation source, related to high-throughput small-molecule X-ray crystallography. As case examples, a series of four novel transition metal complexes with azomethine ligands were selected. The complexes demonstrate somewhat unexpected changes in the coordination geometry and nuclearity in response to the introduction of substituents in the ligand’s periphery. © 2017 by the authors