Intramolecular deactivation processes in complexes of salicylic acid or glycolic acid with Eu(III).

The complexation of Eu(III) by 2-hydroxy benzoic acid (2HB) or glycolic acid (GL) was investigated using steady-state and time-resolved laser spectroscopy. Experiments were carried out in H(2)O as well as in D(2)O in the temperature range of 80K<T<290K. The Eu(III) luminescence spectra and luminescence decay times were evaluated with respect to the temperature dependence of (i) the luminescence decay time tau, (ii) the energy of the D5(0)-->F7(0) transition, (iii) the width of the D5(0)-->F7(0) transition, and (iv) the asymmetry ratio calculated from the luminescence intensities of the D5(0)-->F7(2) and D5(0)-->F7(1) transition, respectively. The differences in ligand-related luminescence quenching are discussed. Based on the temperature dependence of the luminescence decay times an activation energy for the ligand-specific non-radiative deactivation in Eu(III)-2HB or Eu(III)-GL complexes was determined. It is stressed that ligand-specific quenching processes (other than OH quenching induced by water molecules) need to be determined and considered in detail, in order to extract speciation-relevant information from luminescence data (e.g., estimation of the number of water molecules n(H(2)0) in the first coordination sphere of Eu(III)). In case of 2HB, conclusions drawn from the evaluation of the Eu(III) luminescence are compared with results of a X-ray structure analysis. Copyright 2010 Elsevier B.V. All rights reserved.