Polyoxometalates as ligands to synthesize, isolate and characterize compounds of rare isotopes on the microgram scale

Colliard, Ian; Lee, Jonathan R. I.; Colla, Christopher A.; Mason, Harris E.; Sawvel, April M.; Zavarin, Mavrik; Nyman, May; Deblonde, Gauthier J.-P.

doi:10.1038/s41557-022-01018-8

Polyoxometalates as ligands to synthesize, isolate and characterize compounds of rare isotopes on the microgram scale

Journal Article · Thu Sep 01 00:00:00 EDT 2022 · Nature Chemistry

DOI:https://doi.org/10.1038/s41557-022-01018-8· OSTI ID:1886630

Colliard, Ian ^[1]; Lee, Jonathan R. I. ^[2]; Colla, Christopher A. ^[2]; Mason, Harris E. ^[3]; Sawvel, April M. ^[2]; ^[2]; ^[4]; ^[2]

Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Oregon State Univ., Corvallis, OR (United States); University of Notre Dame
Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
Oregon State Univ., Corvallis, OR (United States)

The synthesis and study of radioactive compounds are both inherently limited by their toxicity, cost and isotope scarcity. Traditional methods using small inorganic or organic complexes typically require milligrams of sample—per attempt—which for some isotopes is equivalent to the world’s annual supply. Here we demonstrate that polyoxometalates (POMs) enable the facile formation, crystallization, handling and detailed characterization of metal–ligand complexes from microgram quantities owing to their high molecular weight and controllable solubility properties. Three curium–POM complexes were prepared, using just 1–10 μg per synthesis of the rare isotope ²⁴⁸Cm³⁺, and characterized by single-crystal X-ray diffraction, showing an eight-coordinated Cm³⁺ centre. Moreover, spectrophotometric, fluorescence, NMR and Raman analyses of several f-block element–POM complexes, including ²⁴³Am³⁺ and ²⁴⁸Cm³⁺, showed otherwise unnoticeable differences between their solution versus solid-state chemistry, and actinide versus lanthanide behaviour. Furthermore, this POM-driven strategy represents a viable path to isolate even rarer complexes, notably with actinium or transcalifornium elements.

View Accepted Manuscript (DOE)

Research Organization:: Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States); Los Alamos National Laboratory (LANL), Los Alamos, NM (United States); Univ. of Notre Dame, IN (United States)

Sponsoring Organization:: USDOE National Nuclear Security Administration (NNSA)

Grant/Contract Number:: AC52-07NA27344; NA0003763

OSTI ID:: 1886630

Alternate ID(s):: OSTI ID: 1971304

Report Number(s):: LLNL-JRNL-829648

Journal Information:: Nature Chemistry, Journal Name: Nature Chemistry Journal Issue: 12 Vol. 14; ISSN 1755-4330

Publisher:: Nature Publishing GroupCopyright Statement

Country of Publication:: United States

Language:: English

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CSD 2105623: Experimental Crystal Structure Determination Ian, Colliard,; I., Lee, Jonathan R.; A., Colla, Christopher https://doi.org/10.25505/fiz.icsd.cc28p2bd The current record is supplemented by this dataset	dataset	January 2022
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CSD 2127432: Experimental Crystal Structure Determination Ian, Colliard,; I., Lee, Jonathan R.; A., Colla, Christopher https://doi.org/10.25505/fiz.icsd.cc29drvb The current record is supplemented by this dataset	dataset	January 2022
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Polyoxometalates as ligands to synthesize, isolate and characterize compounds of rare isotopes on the microgram scale

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