A 70‐Year‐Old Mystery in Technetium Chemistry Explained by the New Technetium Polyoxometalate&nbsp;[H 7 O 3 ] 4 [Tc 20 O 68 ] ⋅ 4H 2 O

German, Konstantin E.; Fedoseev, Alexander M.; Grigoriev, Mikhail S.; Kirakosyan, Gayane A.; Dumas, Thomas; Den Auwer, Christophe; Moisy, Philippe; Lawler, Keith V.; Forster, Paul M.; Poineau, Frederic

doi:10.1002/chem.202102035

A 70‐Year‐Old Mystery in Technetium Chemistry Explained by the New Technetium Polyoxometalate [H ₇ O ₃ ] ₄ [Tc ₂₀ O ₆₈ ] ⋅ 4H ₂ O

Journal Article · Wed Aug 04 00:00:00 EDT 2021 · Chemistry - A European Journal

DOI:https://doi.org/10.1002/chem.202102035· OSTI ID:1811927

German, Konstantin E. ^[1]; Fedoseev, Alexander M. ^[1]; Grigoriev, Mikhail S. ^[1]; Kirakosyan, Gayane A. ^[2]; Dumas, Thomas ^[3]; Den Auwer, Christophe ^[4]; Moisy, Philippe ^[3]; Lawler, Keith V. ^[5]; Forster, Paul M. ^[5]; ^[5]

Frumkin Institute of Physical Chemistry and Electrochemistry Russian Academy of Sciences Leninsky pr.31-4 Moscow Russian Federation
Frumkin Institute of Physical Chemistry and Electrochemistry Russian Academy of Sciences Leninsky pr.31-4 Moscow Russian Federation, Kurnakov Institute of General and Inorganic Chemistry Russian Academy of Sciences Moscow Leninsky pr.31 Russian Federation
CEA, DES, ISEC, DMRC Univ Montpellier Marcoule France
Université Côte d'Azur CNRS, ICN 06100 Nice France
Department of Chemistry and Biochemistry University of Nevada Las Vegas 4505 Maryland Parkway Las Vegas NV 89154 USA

Abstract

[H ₇ O ₃ ] ₄ [Tc ₂₀ O ₆₈ ] ⋅ 4H ₂ O [ 1 ] was prepared from an aqueous Tc ₂ O ₇ solution concentrated over anhydrous H ₂ SO ₄ . [Tc ₂₀ O ₆₈ ] ⁴⁻ is the first polyanionic species to be reported for Tc. The unit cell contains one centrosymmetric [Tc ₂₀ O ₆₈ ] ⁴⁻ polyanion as well as hydronium ions and water molecules. The core of the structure consists of four Tc(V)O ₆ octahedra that form a square Tc ₄ O ₄ ring. The four Tc(V)O ₆ octahedra are decorated by sixteen Tc(VII)O ₄ tetrahedra. Calculations show the bonding within the Tc ₄ O ₄ ring to consist of a 3‐center bond formed between each neighboring pair of Tc atoms and their bridging oxygen. Calculations also indicate that a strong d → d electronic transition at 513 nm is the origin of the red color of [ 1 ]. The characterization of red HTcO ₄ solutions by X‐ray absorption spectroscopy has complemented the description of this compound in aqueous solution. The formation mechanisms in solution, including the possible role of technetium's radioactivity in the formation of [ 1 ], are discussed.

View Accepted Manuscript (Publisher)

Sponsoring Organization:: USDOE

Grant/Contract Number:: NA0003948

OSTI ID:: 1811927

Alternate ID(s):: OSTI ID: 1850429
OSTI ID: 23147948

Journal Information:: Chemistry - A European Journal, Journal Name: Chemistry - A European Journal Journal Issue: 54 Vol. 27; ISSN 0947-6539

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Germany

Language:: English

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A 70‐Year‐Old Mystery in Technetium Chemistry Explained by the New Technetium Polyoxometalate [H ₇ O ₃ ] ₄ [Tc ₂₀ O ₆₈ ] ⋅ 4H ₂ O