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<p>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<sub>10</sub>P<sub>2</sub>W<sub>17</sub>O<sub>61</sub>•20H<sub>2</sub>O. Herein we present the single crystal structure of K<sub>16</sub>Tb(IV)(P<sub>2</sub>W<sub>17</sub>O<sub>61</sub>)<sub>2</sub>•39.85H<sub>2</sub>O (Tb(IV)W<sub>34</sub>) 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<sub>34</sub> complexes as +4.</p>

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Structural and spectroscopic characterization of a Tb(IV) polyoxometalate

  • 期刊论文

  • 出版模式：

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  • 发表日期：

    2026年7月16日

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  • Primadi J. Subintoro,
  • Brett Lottes,
  • Felipe A. Pereiro,
  • Nolwenn Mahieu,
  • Alexander M. Brown,
  • S. Genevieve Duggan,
  • Monica S. Mullis,
  • Aldo M. Jordan,
  • Cassandra Gates,
  • Samuel M. Greer,
  • Joshua J. Woods,
  • Rebecca J. Abergel,
  • Jenifer C. Shafer,
  • Daniel K. Unruh,
  • Pere Miró,
  • Benjamin W. Stein,
  • Jennifer N. Wacker,
  • Stosh A. Kozimor,
  • Korey P. Carter

摘要

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, 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 spectroscopy and SQUID magnetometry measurements to confirm the oxidation state of Tb in W34 complexes as +4.