title: Excited state behaviors of the dodecamolybdocerate (IV) anion: (NH4)6H2(CeMo12O42).9H2O.
abstract: The polyoxometalate (NH(4))(6)H(2)(CeMo(12)O(42)).9H(2)O (abbreviated as Ce(IV)Mo(12)) was synthesized, and its Ce(III) form was obtained by exhaustive electrochemical reduction. Both forms are fairly stable in pH 0.0 media. This stability decreases when the pH increases. The Ce(IV) species, in which the central metal is in the f(0) electronic configuration, is found to fluoresce, a feature that is only straightforwardly explained with the Ce(III) state. As the results of a series of experiments converge to confirm the stability of Ce(IV)Mo(12) in the media studied, a suggested rationale is that the emission originates from a higher-energy ligand-to-metal charge transfer and follows a scheme which is ultimately equivalent to the classical metal-centered fluorescence of Ce(III). Detailed studies of the influences of pH and ionic strength were carried out and suggest that protonated and/or ion-paired assemblies are the fluorescent species. A reproducible increase of the fluorescence intensity of Ce(IV)Mo(12) as a function of time was also observed.
authors.affiliation: Laboratoire de Chimie Physique, UMR 8000, CNRS, Université Paris-Sud XI, Bâtiment 350, 91405 Orsay Cedex, France.
authors.forename: Yu Wei
authors.initials: YW
authors.lastname: Lu
authors.forename: Bineta
authors.initials: B
authors.lastname: Keita
authors.forename: Louis
authors.initials: L
authors.lastname: Nadjo
authors.forename: Gérard
authors.initials: G
authors.lastname: Lagarde
authors.forename: Eric
authors.initials: E
authors.lastname: Simoni
authors.forename: Guangjin
authors.initials: G
authors.lastname: Zhang
authors.forename: Galina A
authors.initials: GA
authors.lastname: Tsirlina