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Structural and spectroscopic characterization of a Tb(IV) polyoxometalate

Subintoro, Primadi J. [University of Iowa, Iowa City, IA (United States)]·Lottes, Brett Michael [University of Iowa, Iowa City, IA (United States); Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)]·Pereiro, Felipe Alberto [Los Alamos National Laboratory (LANL), Los Alamos, NM (United States); Colorado School of Mines, Golden, CO (United States)]·Mahieu, Nolwenn [Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)]·Brown, Alexander M. [Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)] (ORCID:000000021497213X)·Duggan, S. Genevieve [University of Iowa, Iowa City, IA (United States)]·Mullis, Monica Suzanne [Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)] (ORCID:0009000719655890)·Jordan, Aldo Michele [Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)]·Gates, Cassandra Leigh [Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)] (ORCID:0000000180902714)·Greer, Samuel Michael [Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)] (ORCID:0000000182253252)·Woods, Joshua J. [Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)] (ORCID:0000000262134093)·Abergel, Rebecca J. [Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States); University of California, Berkeley, CA (United States)] (ORCID:0000000239068761)·Shafer, Jenifer C. [Colorado School of Mines, Golden, CO (United States)]·Unruh, Daniel K. [University of Iowa, Iowa City, IA (United States)] (ORCID:0000000225945786)·Miró, Pere [University of Iowa, Iowa City, IA (United States)]·Stein, Benjamin W. [Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)] (ORCID:0000000203665476)·Wacker, Jennifer N. [Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)] (ORCID:0000000154111986)·Kozimor, Stosh Anthony [Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)] (ORCID:0000000173870507)·Carter, Korey P. [University of Iowa, Iowa City, IA (United States)] (ORCID:0000000341910740)
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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.

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Subintoro, Primadi J. [University of Iowa, Iowa City, IA (United States)], Lottes, Brett Michael [University of Iowa, Iowa City, IA (United States); Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)], Pereiro, Felipe Alberto [Los Alamos National Laboratory (LANL), Los Alamos, NM (United States); Colorado School of Mines, Golden, CO (United States)], Mahieu, Nolwenn [Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)], Brown, Alexander M. [Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)] (ORCID:000000021497213X), Duggan, S. Genevieve [University of Iowa, Iowa City, IA (United States)], Mullis, Monica Suzanne [Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)] (ORCID:0009000719655890), Jordan, Aldo Michele [Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)], Gates, Cassandra Leigh [Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)] (ORCID:0000000180902714), Greer, Samuel Michael [Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)] (ORCID:0000000182253252), Woods, Joshua J. [Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)] (ORCID:0000000262134093), Abergel, Rebecca J. [Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States); University of California, Berkeley, CA (United States)] (ORCID:0000000239068761), Shafer, Jenifer C. [Colorado School of Mines, Golden, CO (United States)], Unruh, Daniel K. [University of Iowa, Iowa City, IA (United States)] (ORCID:0000000225945786), Miró, Pere [University of Iowa, Iowa City, IA (United States)], Stein, Benjamin W. [Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)] (ORCID:0000000203665476), Wacker, Jennifer N. [Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)] (ORCID:0000000154111986), Kozimor, Stosh Anthony [Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)] (ORCID:0000000173870507), Carter, Korey P. [University of Iowa, Iowa City, IA (United States)] (ORCID:0000000341910740). 2026-07-16. Structural and spectroscopic characterization of a Tb(IV) polyoxometalate. https://doi.org/10.1038/s41467-026-75657-7

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