Exploring crown-ether functionalization on the stabilization of hexavalent neptunium

Pyrch, Mikaela M.; Williams, James M.; Forbes, Tori Z.

doi:10.1039/c9cc04393d

Title: Exploring crown-ether functionalization on the stabilization of hexavalent neptunium

Journal Article · 11 July 2019 · ChemComm

DOI: https://doi.org/10.1039/c9cc04393d · OSTI ID:1668731

Pyrch, Mikaela M. ^[1]; Williams, James M. ^[1];

^[1]

University of Iowa, Iowa City, IA (United States)

Crown-ether molecules are used in radiochemical separations due to their high selectivity for a range of metal cations. Previous investigations regarding the interactions of 18-crown-6 (18C6) with ²³⁷Np suggested the formation of a Np(V) inclusion complex, but also reported rapid reduction of Np(VI) to Np(V) in the presence of the ether molecule. Herein, we investigate the impact of crown ether functionalization by exploring the Np(V) and Np(VI) dicyclohexano-18-crown-6 (DCH-18C6) systems. Two [X(DCH-18C6)]₂[Np(VI)O₂Cl₄] compounds (X = K (1) and Na (2)) were crystallized and characterized by single crystal X-ray diffraction and Raman spectroscopy. Additional studies of Np(VI), Np(V), and Np(V)/Np(VI) in solution indicated redox stability in the presence of functionalized crowns and preferential crystallization of Np(VI) DCH-18C6 solids. Furthermore, these results indicate that functionalization of the crown can lead to higher resistance to radiolysis and increased stability of the Np(VI) oxidation state in solution.

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Research Organization:: Univ. of Iowa, Iowa City, IA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0013980

OSTI ID:: 1668731

Alternate ID(s):: OSTI ID: 1543020

Journal Information:: ChemComm, Vol. 55, Issue 63; ISSN 1359-7345

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 10 works

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Cited By (1)

Impacts of hydrogen bonding interactions with Np( v / vi )O ₂ Cl ₄ complexes: vibrational spectroscopy, redox behavior, and computational analysis Pyrch, Mikaela M.; Bjorklund, Jennifer L.; Williams, James M. Dalton Transactions, Vol. 49, Issue 20 https://doi.org/10.1039/d0dt00848f	journal	January 2020

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Neptunium
crown ether
functionalization
redox stabilization

CCDC 1921583: Experimental Crystal Structure Determination M., Pyrch, Mikaela; M., Williams, James; Z., Forbes, Tori https://doi.org/10.5517/ccdc.csd.cc22hkkq The current record is supplemented by this dataset	dataset	January 2019
CCDC 1921584: Experimental Crystal Structure Determination M., Pyrch, Mikaela; M., Williams, James; Z., Forbes, Tori https://doi.org/10.5517/ccdc.csd.cc22hklr The current record is supplemented by this dataset	dataset	January 2019