7 resultados para Trivalent ion

em Repositório Institucional UNESP - Universidade Estadual Paulista "Julio de Mesquita Filho"


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Photoluminescence and photo-excited conductivity data as well as structural analysis are presented for sol-gel SnO2 thin films doped with rare earth ions Eu3+ and Er3+, deposited by sol-gel-dip-coating technique. Photoluminescence spectra are obtained under excitation with various types of monochromatic light sources, such as Kr+, Ar+ and Nd:YAG lasers, besides a Xe lamp plus a selective monochromator with UV grating. The luminescence fine structure is rather different depending on the location of the rare-earth doping, at lattice symmetric sites or segregated at the asymmetric grain boundary layer sites. The decay of photo-excited conductivity also shows different trapping rate depending on the rare-earth concentration. For Er-doped films, above the saturation limit, the evaluated capture energy is higher than for films with concentration below the limit, in good agreement with the different behaviour obtained from luminescence data. For Eu-doped films, the difference in the capture energy is not so evident in these materials with nanoscocopic crystallites, even though the luminescence spectra are rather distinct. It seems that grain boundary scattering plays a major role in Eu-doped SnO2 films. Structural evaluation helps to interpret the electro-optical data. © 2010 IOP Publishing Ltd.

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Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

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We present photoluminescence and decay of photo excited conductivity data for sol-gel SnO(2) thin films doped with rare earth ions Eu(3+) and Er(3+), a material with nanoscopic crystallites. Photoluminescence spectra are obtained under excitation with several monochromatic light sources, such as Kr(+) and Ar(+) lasers, Xe lamp plus a selective monochromator with UV grating, and the fourth harmonic of a Nd: YAG laser (4.65eV), which assures band-to-band transition and energy transfer to the ion located at matrix sites, substitutional to Sn(4+). The luminescence structure is rather different depending on the location of the rare-earth doping, at lattice symmetric sites or segregated at grain boundary layer, where it is placed in asymmetric sites. The decay of photo-excited conductivity also shows different trapping rate depending on the rare-earth concentration. For Er-doped films, above the saturation limit, the evaluated capture energy is higher than for films with concentration below the limit, in good agreement with the different behaviour obtained from luminescence data. For Eu-doped films, the difference between capture energy and grain boundary barrier is not so evident, even though the luminescence spectra are rather distinct.

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The protonation constants of 4-methylbenzylidenepyruvate (4Me-BP) and 4-isopropylbenzylidenepyruvate (4IP-BP) as well as the stability constants of their binary 1:1 complexes with Cu(II), La(III), Pr(III), Sm(III), Eu(III), Yb(III), Sc(III) and Th(IV) have been determined spectrophotometrically in aqueous solution at 25°C and ionic strength 0.500 M, maintained with sodium perchlorate. For all metal ions considered, the stability changes move in the same direction as the pKa of the ligands. Linear free energy relationships, as applied to oxygen donor substances, suggest the -COCOO- moiety as the metal binding site of the ligands. The results are discussed mainly taking into account that benzylidenepyruvates, besides the α-keto canonical form, may display other forms in aqueous solution with changing pH and the possible occurrence of extra intra-ligand charge polarization, induced by metal ions.

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4-Dimethylaminocinnamylidenepyruvic acid (H-DMCP)and its sodium salt (Na-DMCP) have been synthesized and characterized. The protonation constant of DMCP as well as the stability constants of its binary 1:1 complexes with trivalent lanthanides (except Pm), Yttrium(III), Scandium(III), Thorium(IV) and Uranium(VI) were determined in an aqueous medium at 25°C and ionic strength 0.500 M. The mode of coordination of this ligand is discussed.

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Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

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The protonation constants of benzylidenepyruvate, 2-chloro-, 4-chlorobenzylidinepyruvate and cinnamylidenepyruvate as well as the stability constants of their binary 1:1 complexes with Cu(II), La(III), Pr(III), Sm(III), Lu(III), Sc(III) and Th(IV) have been determined spectrophotometrically in an aqueous medium at 25 °C and ionic strength 0.500 M, held with sodium perchlorate. Coordination centres in the aforementioned ligands are suggested. © 1995.