title: Synthesis, crystal structure, and modelling of a new tetramer complex of europium.
abstract: A new compound with the formula [Eu4(ETA)9(OH)3(H2O)3)], where ETA is ethyl 4,4,4-trifluoroacetoacetate, has been synthesized and investigated by photoluminescence spectroscopy. The compound was characterized by means of chemical analysis, vibrational (IR), UV-vis absorption, and luminescence spectroscopies, and X-ray crystallography. The crystal structure of the [Eu4(ETA)9(OH)3(H2O)3)] complex in the solid state, determined by X-ray diffraction analysis, revealed that it crystallizes in the triclinic crystal system, space group P, with four crystallographically independent europium centers. From these structural data, the ground-state geometry of the tetramer has been calculated by using the Sparkle/AM1 model. The emission spectrum shows the characteristic transitions of the Eu3+ ion. The features displayed by the5D0-->7F0 transition in the emission spectrum are consistent with the Eu3+ ion occupying four different sites in chemical environments of low symmetries, in agreement with the X-ray data and the optimized geometry obtained from the Sparkle/AM1 model. These structural results have allowed the theoretical calculation of 4f-4f intensity parameters, including the forced electric dipole and dynamic coupling mechanisms as well as ligand singlet and triplet states, in good agreement with experiment.
authors.affiliation: Departamento de Química Fundamental and Centro de Ciências Exatas e da Natureza, Universidade Federal de Pernambuco, Cidade Universitária, 50590-470 Recife-PE, Brazil.
authors.forename: Ana Paula
authors.initials: AP
authors.lastname: Souza
authors.forename: Filipe A Almeida
authors.initials: FA
authors.lastname: Paz
authors.forename: Ricardo O
authors.initials: RO
authors.lastname: Freire
authors.forename: Luís D
authors.initials: LD
authors.lastname: Carlos
authors.forename: Oscar L
authors.initials: OL
authors.lastname: Malta
authors.forename: S
authors.initials: S
authors.lastname: Alves
authors.forename: Gilberto F
authors.initials: GF
authors.lastname: de Sá