Preparation, crystal structure and optical spectroscopy of the rare earth complexes (RE 3+=Sm, Eu, Gd and Tb) with 2-thiopheneacetate anion

Abstract

Rare earth complexes with the formulae Sm(TPAC) 3·3H 2O, Eu 2(TPAC) 6·5.25H 2O and RE(TPAC) 3·3.5H 2O (where RE=Gd and Tb), and TPAC=2-thiopheneacetate) have been synthesized and characterized by complexometric titration, elemental analyses, infrared spectroscopy, and X-ray crystallography. Infrared data suggested the presence of both bridging and chelating TPAC anions. The crystal structure of the [Eu 2(TPAC) 6·(H 2O) 3]·2.25H 2O complex in the solid state, determined by X-ray diffraction, revealed that it crystallizes in the orthorhombic crystal system (space group Aba2), with two crystallographically independent Eu 3+ centers (Eu1 and Eu2). These europium centers are held together by one bidentate bridging and two tridentate bridging carboxylate groups. The existence of two Eu 3+ centers was also supported by the emission spectrum. The luminescence properties of the RE–TPAC complexes were investigated by measuring the excitation and emission spectra, and the intramolecular ligand-to-rare earth energy transfer mechanisms were discussed. The emission spectra of the Eu 3+ and Tb 3+ ions displayed only narrow bands arising from 5D 0→ 7F 0 and 5D 0→ 7F 0–4 transitions, respectively, indicating an efficient luminescence sensitization of these ions by the TPAC ‘antenna’. On the other hand, the emission spectrum of the Sm 3+-complex displayed a broad band from the phosphorescence of the TPAC ligand which overlapped the 4f 5-intraconfigurational transitions. The theoretical intensity parameters Ω λ ( λ=2 and 4), maximum splitting of the 7F 1 state (Δ E) and the ratio between the 5D 0→ 7F 0 and 5D 0→ 7F 2 transition intensities ( R 02) were calculated based on the X-ray crystalline structure for the Eu 3+-complex, and a comparison with experimental data were made. The emission quantum efficiency ( η) of the D 5 emitting level of the Eu 3+ ion was also determined.