Luminescent and magnetic materials with a high content of Eu(3+)-EDTA complexes.

Bifunctional optical magnetic materials with a high europium content have been prepared. Chelating groups were introduced on the Fe3O4 surface with organosilanes containing ethylenediaminetetraacetic acid (EDTA) derivatives, which were previously prepared via a reaction between EDTA-dianhydride and aminoalkoxysilane agents: 3-(trimethoxysilyl)propylamine (1N), N-[3(trimethoxysilyl)propyl]ethylenediamine (2N) and N(1)-(3-trimethoxysilylpropyl)diethylenetriamine) (3N). The first coordination sphere of Ln-EDTA complexes present on the modified surfaces of Fe3O4 particles was completed by addition of ß-diketonate ligands (tta: thenoyltrifluoroacetone, dbm: dibenzoylmethane, bzac: benzoylacetone and acac: acetylacetone) in order to improve their luminescence properties. The materials were characterized by powder X-ray diffraction (XRD), vibrating sample magnetometry (VSM), scanning electron microscopy (SEM), transmission electron microscopy (TEM), thermogravimetric analysis (TGA), and wavelength dispersive X-ray fluorescence (WDXRF) and Fourier-transform infrared (FT-IR) spectroscopy as well as by zeta potential measurements and luminescence spectroscopy. The hybrid materials exhibited intense red emission, which can be assigned to the 4f-4f transitions of the Eu(3+) ion, indicating an efficient intramolecular ligand-to-metal energy transfer. The experimental intensity parameters (Ω2 and Ω4), lifetimes (τ), as well as radiative (Arad) and non-radiative (Anrad) decay rates of the Eu(3+) ion were determined and discussed. The strategies used to obtain these materials may contribute to the development of several bifunctional systems for practical applications.

Intramolecular energy transfer through charge transfer state in lanthanide compounds: a theoretical approach.

A theoretical approach for the intramolecular energy transfer process involving the ligand-to-metal charge transfer (LMCT) state in lanthanide compounds is developed. Considering a two-electron interaction, both the direct Coulomb and exchange interactions are taken into account, leading to expressions from which selection rules may be derived and transfer rates may be calculated. These selection rules show that the direct Coulomb and exchange mechanisms are complementary, in the same way as obtained in previous works for the case of ligand-lanthanide ion energy transfer processes. An important result from numerical estimates is that the channel ligand-LMCT state is by far the dominant case, leading to transfer rates higher than for the channel lanthanide ion-LMCT state by several orders of magnitude. The analysis of the emission quantum yield as a function of the relative energy position of the LMCT state in a typical Eu(3+) compound allows the identification of two quenching regions, the most pronounced one occurring close to the lower ligand triplet level.