Work

Isolation and Characterization of Tb(IV) in Aqueous Media via Polyoxometalate Encapsulation

Year: 2025

Type: preprint

Abstract: There has been a renaissance in high valent lanthanide chemistry, which has resulted in the first examples of tetravalent praseodymium (Pr) and terbium (Tb) in molecular systems. These feats have been achieved with tailored ligands that facilitate tetravalent lanthanide stability in non-aqueous conditions. The next step in realizing the potential of high valent lanthanide chemistry is moving towards complexes that are stable in ambient and aqueous conditions. In this investigation, we have advanced this paradigm by obtaining definitive evidence of the isolation of Tb(IV) in a molecular system under aqueous conditions utilizing the lacunary Wells-Dawson polyoxometalate, K10P2W17O61•20H2O. Herein we present the single crystal structure of K16Tb(IV)(P2W17O61)2•39.85H2O (Tb(IV)W34) as well as extensive spectroscopic evidence obtained via UV-Vis-NIR, X-ray absorption near edge spectroscopy, continuous wave X-band electron paramagnetic resonance spectroscopies and SQUID magnetometry measurements to confirm the oxidation state of Tb in W34 complexes as +4.

Source: ChemRxiv

DOI: 10.26434/chemrxiv-2025-nqb6x

Authors: Primadi Subintoro, Brett Lottes, Felipe Pereiro, Nolwenn Mahieu, Alexander Brown, S. Genevieve Duggan, Monica Mullis, Aldo Jordan, Cassandra Gates, Samuel Greer, Joshua Woods, Rebecca Abergel, Jenifer Shafer, Daniel Unruh, Pere Miro, Benjamin Stein, Jennifer Wacker, Stosh Kozimor, Korey Carter

Institutions: University of Iowa, Los Alamos National Laboratory, Colorado School of Mines, Lawrence Berkeley National Laboratory, University of California, Berkeley

Language: English

Topic: Polyoxometalates: Synthesis and Applications

Subfield: Materials Chemistry

Field: Materials Science

Domain: Physical Sciences

Open Access status: green

Funders: National Science Foundation, U.S. Department of Energy, Oak Ridge Associated Universities, Glenn T. Seaborg Institute, Office of Science, National Nuclear Security Administration, Oak Ridge Institute for Science and Education, Division of Chemistry, Basic Energy Sciences, Workforce Development for Teachers and Scientists, Chemical Sciences, Geosciences, and Biosciences Division, Lawrence Berkeley National Laboratory, Los Alamos National Laboratory, SLAC National Accelerator Laboratory

Awards: G1071216263, G1079818582, G1143651532, G1153001495, G1229526393, G1286236842, G1286251239, G1311044274, G1451874870, G1519943830, G1538770391, G17040919, G1825462127, G1863003419, G2037563265, G22000355, G2371548206, G2438174618, G2505738042, G2618837358, G262532246, G2900453181, G2917895714, G3005031308, G303061748, G30714459, G3884951186, G3934797364, G419881185, G4235786860, G42916606, TRANSFORMING CRITICAL MATERIALS SEPARATIONS THROUGH METAL-OXO CLUSTER CHEMISTRY, G4501827968, G4654690619, G467269851, G473123490, G473396326, G495301720, G498139845, G5070048936, G5094606986, G515206079, G5570207115, MANIPULATION OF LIGAND ELECTRONIC STRUCTURE TO CONTROL F-ELEMENT COVALENCY, G5977822009, G601061201, G6017181652, G6371445390, MRI: Acquisition of a Variable-Temperature, Dual-Wavelength, Single-Crystal X-Ray Diffractometer, G650090426, G6550344761, G6652958823, G7283024673, G7331630580, G7354628648, G7619220232, G8382000481, G8437677540, G8570346810, G911061179

OpenAlex ID: W4416143904

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Cited by: 1

Related to: 10