Luminescence from cerium(iii) acetate complexes in aqueous solution: considerations on the nature of carboxylate binding to trivalent lanthanides

Abstract

The luminescence of cerium(III) has been studied in aqueous solutions in the presence of acetate ion. In contrast to previous reports that cerium(III) carboxylate complexes do not luminesce, a weak emission is observed, which has a similar spectrum to the aquo cerium(III) species but a much shorter lifetime. Results from a variety of studies on complexation of various trivalent lanthanide ions with carboxylates, including NMR spectral and relaxation measurements, molecular mechanics calculations, deuterium isotope effects on Tb(III) luminescence lifetimes, together with literature data strongly suggest that the dominant mode of complexation between carboxylates and trivalent lanthanides involves a weak, predominantly bidentate, binding to the metal cation. We suggest that the observed emission arises from a 1 : 1 cerium acetate species involving such bidentate coordination.