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Excited State Behaviors of the Dodecamolybdocerate (IV) Anion: (NH_4)_6H_2(CeMo_12O_42)·9H_2O

Abstract : The polyoxometalate (NH4)6H2(CeMo12O42)·9H2O (abbreviated as CeIVMo12) 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 f0 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 CeIVMo12 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 CeIVMo12 as a function of time was also observed.
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Submitted on : Tuesday, April 22, 2008 - 5:03:21 PM
Last modification on : Wednesday, September 16, 2020 - 4:32:00 PM

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Yu Wei Lu, B. Keita, L. Nadjo, G. Lagarde, E. Simoni, et al.. Excited State Behaviors of the Dodecamolybdocerate (IV) Anion: (NH_4)_6H_2(CeMo_12O_42)·9H_2O. Journal of Physical Chemistry B, American Chemical Society, 2006, 110, pp.15633. ⟨10.1021/jp0605653⟩. ⟨in2p3-00275203⟩

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