IFLP   13074
INSTITUTO DE FISICA LA PLATA
Unidad Ejecutora - UE
congresos y reuniones científicas
Título:
Metal coordination study in Crown thioethers through DFT calculations and hyperfine parameters
Autor/es:
R. NASCIMENTO; F. CAMARGO DALMATTI ALVES DE LIMA; M. BROWN GONÇALVES; L. A: ERRICO; H. M. PETRILLI
Lugar:
Campos de Jordao
Reunión:
Congreso; XIII Encontro da Sociedade Brasileira de Materiais (SBPMat XIII); 2013
Institución organizadora:
Sociedade Brasileira de Materiais
Resumen:
The understanding of metal coordination of the chelates have high impact in many different areas, such as solubilization of inorganic compounds, separation of inorganic salts, liquid-membrane separation, liquid-liquid extraction, ion sensitive electrodes, and in organic synthesis as phase transfer reagents. Hyperfine techniques can be used to elucidate local environments of heterocyclic ligands as Crown thioether which its ion-ligand affinity can be correlated with the macrocycle hole size, shape and plasticity. In this work structural and electronic properties of [C12H24S6X], [C13H26S6OX] and [C14H28S6OX] (X: Ag+, Cd+/2+) Crown thioether complexes are investigated within the framework of the Density Functional Theory (DFT) using the Projector Augmented Wave (PAW) method. The theoretical results are then compared with Timedependent Perturbed Angular Correlations (TDPAC) experiments performed using the 111Ag→111Cd probe to understand the metal coordination. This comparison allows to state that the measured EFG at the Cd sites correspond to the case of +2 charge state in the Ag+ coordination sphere (i.e., before the structural relaxations are completed). These results are discussed in terms of the characteristics of the TDPAC 111Ag→111Cd probe and the time window of the measurement.
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