Estudo do comportamento estrutural, vibracional e térmico do complexo bis(L-glutaminato) de cobre(II)

Abstract

Crystals of pure amino acids or complexed with salts or with transition metals can exhibit important electrical, magnetic, optic and others physical properties. Copper(II) complexes of amino acids have been widely studied as potentials medicines and dietary supplementation, so the knowledge about the metal-ligand sites, thermal stability and behavior of these complexes are important subjects of study. Although Raman spectroscopy can help to elucidate the nature of these interactions in the crystal there is little information on the vibrational modes of this compound in the literature and there are no temperature dependent Raman data. In addition, there is no temperature-dependent X-ray diffraction study of this material. We report here Raman Spectroscopy and Powder X-ray Diffraction measurements results, both as a function of temperature and as a way of studying the thermal stability of the material. After the synthesis of the sample and confirmation of its crystal structure by Powder X-ray Diffraction, Raman measurements were performed in the 70–3600 cm-1 spectral region as a function of temperature from 10 up to 300 K. Some peaks become more evident during the cooling, due to a decrease in width and an increase in intensity. There is a discontinuity in the wavenumbers evolution around 110 K, that should be associated with a conformation of the structure. Optimized geometry and vibrational frequencies were obtained by means the Density Functional Theory and for the first time the analysis of the vibrational modes was done in terms of the Potential Energy Distribution. X-ray diffraction measurements as a function of temperature and Rietveld refinement showed discontinuities in the lattice parameters and degradation around 493 K (at air atmosphere) and 513 K (under vacuum). These results were corroborated by thermal analysis which indicates that the compound is stable up to about 493 K (220ºC).