Experimental Evidence of the Occurrence of Intramolecular Electron Transfer in Catalyzed 1,2-Dioxetane Decomposition

The activation parameters for the thermal decomposition of 13 acridinium-substituted 1,2-dioxetanes, bearing an aromatic moiety, were determined and their chemiluminescence emission quantum yields estimated, utilizing in situ photosensitized 1,2-dioxetane generation and observation of its thermal decomposition kinetics, without isolation of these highly unstable cyclic peroxides. Decomposition rate constants show linear free-energy correlation for electron-withdrawing substituents, with a Hammett reaction constant of rho = 1.3 +/- 0.1, indicating the occurrence of an intramolecular electron transfer from the acridinium moiety to the 1,2-dioxetane ring, as postulated by the intramolecular chemically initiated electron exchange luminescence (CIEEL) mechanism. Emission quantum yield behavior can also be rationalized on the basis of the intramolecular CIEEL mechanism, additionally evidencing its occurrence in this transformation. Both relations constitute the first experimental evidence for the occurrence of the postulated intramolecular electron transfer in the catalyzed and induced decomposition of properly substituted 1,2-dioxetanes.

Thermoluminescence and synchrotron radiation studies on the persistent luminescence of BaAl(2)O(4)/Eu(2+),Dy(3+)

The persistent luminescence materials, barium aluminates doped with Eu(2+) and Dy(3+) (BaAl(2)O(4): Eu(2+),Dy(3+)), were prepared with the combustion synthesis at temperatures between 400 and 600 degrees C as well as with the solid state reaction at 1500 degrees C. The concentrations of Eu(2+)/Dy(3+) (in mol% of the Ba amount) ranged from 0.1/0.1 to 1.0/3.0. The electronic and defect energy level structures were studied with thermoluminescence (TL) and synchrotron radiation (SR) spectroscopies: UV-VUV excitation and emission, as well as with X-ray absorption near-edge structure (XANES) methods. Theoretical calculations using the density functional theory (DFT) were carried out in order to compare with the experimental data. (C) 2010 Elsevier Inc. All rights reserved.

Ring Contraction of 1,2-Dihydronaphthalenes Promoted by Thallium(III) in Acetonitrile: A Diastereoselective Approach to Indanes

trans-1,3-Disubstituted indanes are conveniently accessed by a stereoselective ring contraction of 1,2-dihydronaphthalenes upon treatment with thallium(III) nitrate (TTN) in acetonitrile. Under these conditions, the oxidative rearrangement of either di- or trisubstituted double bonds is possible.

CuO and CuO-ZnO catalysts supported on CeO(2) and CeO(2)-LaO(3) for low temperature water-gas shift reaction

This paper describes an investigation on CuO and CuO-ZnO catalysts supported on CeO(2) and CeO(2)-La(2)O(3) oxides, which were designed for the low temperature water-gas shift reaction (WGSR). Bulk catalysts were prepared by co-precipitation of metal nitrates and characterized by energy-dispersive spectroscopy (EDS), X-ray diffraction (XRD), surface area (by the BET method), X-ray photoelectron spectroscopy (XPS), and in situ X-ray absorption near edge structure (XANES). The catalysts` activities were tested in the forward WGSR, and the CuO/CeO(2) catalyst presented the best catalytic performance. The reasons for this are twofold: (1) the presence of Zn inhibits the interaction between Cu and Ce ions, and (2) lanthanum oxide forms a solid solution with cerium oxide, which will cause a decrease in the surface area of the catalysts. Also the CuO/CeO(2) catalyst presented the highest Cu content on the surface, which could influence its catalytic behavior. Additionally, the Cu and Cu(1+) species could influence the catalytic activity via a reduction-oxidation mechanism, corroborating to the best catalytic performance of the Cu/Ce catalyst. (c) 2010 Elsevier B.V. All rights reserved.

Towards to the trans-bromination of 2-styrylpyridine with a palladacycle intermediary and structure analysis for trans-1,2-dibromo-2-styrylpyridine

The simple halogenation of alkynes in conventional organic reactions gives a blend of cis and trans isomers. It is proposed then, a synthesis of stereospecific halogenation of alkynes in trans position, using palladacycle as intermediaries. The recrystallization of the compound obtained by bromination of 2-Styrylpyridine, with cyclepalladium intermediary results in a single crystal, which is subjected to X-ray diffraction. The crystal packing is established through weak interactions of three types. The first one is of the type pi x pi interactions, from symmetry operation, between the centroids. The second one is of the type C-X center dot center dot center dot pi interactions. And the last type is an anomalous intermolecular interaction between halogens, C-X center dot center dot center dot X-C, with bond distances smaller than the sum of the van der Waals radii. The conformation on the C=C bond is trans and the dihedral angle between the aromatic rings is (with esd approximate) 18.1(3)degrees. (C) 2010 Elsevier B.V. All rights reserved.