Structural and spectroscopic characterization of a Tb(IV) polyoxometalate
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 advance this paradigm by obtaining definitive evidence of Tb(IV) in a molecular system under aqueous conditions utilizing the lacunary Wells-Dawson polyoxometalate, K 10 P 2 W 17 O 61 •20H 2 O. Herein we present the single crystal structure of K 16 Tb(IV)(P 2 W 17 O 61 ) 2 •39.85H 2 O (Tb(IV)W 34 ) as well as extensive spectroscopic evidence obtained via UV–Vis-NIR, X-ray absorption near edge spectroscopy, continuous wave X-band electron paramagnetic resonance spectroscopy and SQUID magnetometry measurements to confirm the oxidation state of Tb in W 34 complexes as +4.
Authors
- Benjamin W. Stein (ORCID: https://orcid.org/0000-0002-0366-5476)
- Joshua J. Woods (ORCID: https://orcid.org/0000-0002-6213-4093)
- Alexander M. Brown (ORCID: https://orcid.org/0000-0002-1497-213X)
- Jennifer N. Wacker (ORCID: https://orcid.org/0000-0001-5411-1986)
- Samuel M. Greer (ORCID: https://orcid.org/0000-0001-8225-3252)
- Cassandra Gates (ORCID: https://orcid.org/0000-0001-8090-2714)
- Rebecca J. Abergel (ORCID: https://orcid.org/0000-0002-3906-8761)
- Jenifer C. Shafer (ORCID: https://orcid.org/0000-0001-9702-1534)
- Korey P. Carter (ORCID: https://orcid.org/0000-0003-4191-0740)
- Nolwenn Mahieu (ORCID: https://orcid.org/0000-0003-2280-3616)
- Aldo Jordan
- Stosh A. Kozimor (ORCID: https://orcid.org/0000-0001-7387-0507)
- Pere Miró (ORCID: https://orcid.org/0000-0002-3281-0708)
- Daniel K. Unruh (ORCID: https://orcid.org/0000-0002-2594-5786)
- Brett Lottes
- Primadi Subintoro
- Felipe A. Pereiro (ORCID: https://orcid.org/0009-0008-6536-0388)
- Monica S. Mullis
- S Genevieve Duggan
Institutions
- University of Iowa (US)
- Los Alamos National Laboratory (US)
- Lawrence Berkeley National Laboratory (US)
- Colorado School of Mines (US)
- Los Alamos National Security (United States) (US)
- University of California, Berkeley (US)
Publication Details
- Journal
- Nature Communications
- Published
- 2026-07-16
- DOI
- https://doi.org/10.1038/s41467-026-75657-7
- Primary Topic
- Polyoxometalates: Synthesis and Applications
- Type
- article
- Field-Weighted Citation Impact
- 0.00
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