Abstract
Harnessing Polyoxometalate Coordination Chemistry to Stabilize Lanthanides and Actinides in the +4 Oxidation State
Meeting abstracts (Electrochemical Society), Vol.MA2025-02(61), pp.2845-2845
11/24/2025
DOI: 10.1149/MA2025-02612845mtgabs
Abstract
F-element polyoxometalate (POM) complexes offer unmatched promise in multiple fields including quantum information science, critical material separations, and catalysis. At the core of each of these efforts is the ability to control metal-ion electronic structure and redox chemistry, which dictate how spins interact within molecules and can provide a platform for streamlining rare-earth and minor actinide separations relevant across multiple industries. The rigid lacunary Wells Dawson anion (W 34 ) is the POM ligand that has made these efforts possible, and this is a species with a known propensity for binding to M(IV) cations that offers a chelation-based pathway to significantly shift metal-ion redox potentials. This has provided a route to access the first, stable Tb(IV) complex in aqueous conditions and the first example of a Bk(IV) coordination complex characterized in the solid-state. The Tb oxidation state in the Tb(IV)W 34 complex was experimentally confirmed via X-ray absorption spectroscopy and cyclic voltammetry experiments, while berkelium oxidation state changes were monitored through a combination of solid-state structural parameter shifts, in-growth and movement of peaks in single crystal absorption and fluorescence spectra, and the presence of detectable signals via X-band electron paramagnetic resonance spectroscopy experiments. Both POM systems feature f 7 electron configurations that have enabled detailed electronic structure study and spectroscopic results from these efforts as well as initial results from lab scale POM driven Tb/Dy separations will be presented as well.
Details
- Title: Subtitle
- Harnessing Polyoxometalate Coordination Chemistry to Stabilize Lanthanides and Actinides in the +4 Oxidation State
- Creators
- Primadi SubintoroBrett LottesFelipe PereiroAldo JordanCassandra GatesSamuel Greer - Los Alamos National LaboratoryBenjamin W Stein - Los Alamos National LaboratoryStosh KozimorJoshua Woods - Lawrence Berkeley National LaboratoryJennifer N WackerKorey Carter
- Resource Type
- Abstract
- Publication Details
- Meeting abstracts (Electrochemical Society), Vol.MA2025-02(61), pp.2845-2845
- DOI
- 10.1149/MA2025-02612845mtgabs
- ISSN
- 2151-2043
- eISSN
- 2151-2035
- Language
- English
- Date published
- 11/24/2025
- Academic Unit
- Chemistry
- Record Identifier
- 9985034928602771
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