Complexes between lanthanide picrates and N,N-dimethylacetamide (DMA): synthesis, characterization, spectroscopic studies and thermal behavior

by Paixão de, Carlos Vital

Abstract (Summary)
The preparation and characterization of lanthanide picrate compounds with N, N - dimethylacetamide (DMA) are described in this thesis. The composition is: Ln(pic)3.3DMA, Ln = La(III) - Lu(III) e Y(III). The coordination of the anion, as bidentate, to the central ions was suggested by conductance data in acetonitrile and nitromethane solutions and by the vibrational I.R. modes of ?sNO2 and ?asNO2. The DMA coordination through the carbonyl oxygen was suggested by the ?CO shift to lower energies. Visible absorption Nd(III) spectra indicate a non cubic site around the central ion and an electrostatic character for metal ligands bonds. The Eu(III) emission spectrum suggested the existence of tricapped trigonal prism and D3h microsymmetry around the central ion. The Sm(III) emission spectrum showed a resonance of the 6H7/2 electronic levels with the phonon density of the compound, with appearance of satellite peaks in the 4G5/2 ? 6H7/2 transition. The energy levels in transfer were estimated through the excitation and emission of La(III), Eu(III), Gd(III) and Lu(III). The lifetimes of the Eu(III) 5D0, Sm(III) 4G5/2 levels and the emissions of the picrate anions were measured. The relative quantum efficiency of some transitions were calculated. X - ray single crystal diffraction studies for La(III) e Sm(III) compounds confirmed the bidentate coordination of the picrates and the DMA coordination through the carbonyl oxygen. TG, DTG e DSC techniques were employed to study the thermal behavior of the compounds.
This document abstract is also available in Portuguese.
Bibliographical Information:

Advisor:Geraldo Vicentini; Alcídio Abrão; Hermi Felinto de Brito; Marisa Spirandelli Crespi; Manfredo Horner; Geraldo Vicentini

School:Universidade de São Paulo

School Location:Brazil

Source Type:Master's Thesis

Keywords: Dimethylacetamide Dimetilacetamida Inorganic chemistry Lantanídeos Luminescence Picrates Picratos Spectroscopy


Date of Publication:07/21/1997

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