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Title: Cation-Directed Isomerization of the U 28 Uranyl-Peroxide Cluster: Cation-Directed Isomerization of the U 28 Uranyl-Peroxide Cluster

Abstract

The conformational dynamics of nanometer-sized actinide ions are exceptionally sensitive to the choice of counter-cations. A new means of following these dynamics in solution is presented that follows 1H NMR signals. The direct bond between hydrogen and phosphorus atoms in the bridging phosphonic groups of the [(UO 2) 28(O 2) 20(PHO 3) 24(H 2O) 12] 32– (U28) cluster allows unparalleled recording of the orientations of these bridges in situ. The µ 3-PHO 3 bridges are organized into two supersets of conformers (facing inward vs. outward from the cluster), but each of these supersets additionally have four subsets that can be identified based upon orientations of the lone pairs of electrons in the associated oxygen atoms. The ensemble of these subsets changes over days or weeks depending upon bulk solution chemistry, temperature, and pressure. They also reflect cations trapped within the molecule. The 1H NMR spectra at room temperature indicate that the molecular orientation of this enormous ion tunes itself in response to solution composition, which suggests a strategy for selecting host–guest combinations.

Authors:
ORCiD logo [1];  [2];  [2];  [1];  [3];  [4];  [5];  [6]
  1. Southern Oregon Univ., Ashland, OR (United States). Dept. of Chemistry
  2. Univ. of California, Davis, CA (United States). Dept. of Earth and Planetary Sciences
  3. Univ. of Notre Dame, IN (United States). Dept. of Civil and Environmental Engineering and Earth Sciences
  4. Univ. of Notre Dame, IN (United States). Dept. of Chemistry and Biochemistry
  5. Univ. of Notre Dame, IN (United States). Dept. of Civil and Environmental Engineering and Earth Sciences, Dept. of Chemistry and Biochemistry
  6. Univ. of California, Davis, CA (United States). Dept. of Earth and Planetary Sciences, and Dept. of Chemistry
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Materials Science of Actinides (MSA)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1470042
Alternate Identifier(s):
OSTI ID: 1398815
Grant/Contract Number:  
[SC0001089]
Resource Type:
Accepted Manuscript
Journal Name:
European Journal of Inorganic Chemistry
Additional Journal Information:
[ Journal Volume: 2017; Journal Issue: 46; Related Information: MSA partners with University of Notre Dame (lead); University of California, Davis; Florida State University; George Washington University; University of Michigan; University of Minnesota; Oak Ridge National Laboratory; Oregon state University; Rensselaer Polytechnic Institute; Savannah River National Laboratory]; Journal ID: ISSN 1434-1948
Publisher:
ChemPubSoc Europe
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; nuclear (including radiation effects); materials and chemistry by design; synthesis (novel materials); synthesis (self-assembly)

Citation Formats

Oliveri, Anna F., Colla, Christopher A., Callahan, Joseph R., Bogard, Gwendolyn, Qiu, Jie, Dembowski, Mateusz, Burns, Peter C., and Casey, William H. Cation-Directed Isomerization of the U28 Uranyl-Peroxide Cluster: Cation-Directed Isomerization of the U28 Uranyl-Peroxide Cluster. United States: N. p., 2017. Web. doi:10.1002/ejic.201701074.
Oliveri, Anna F., Colla, Christopher A., Callahan, Joseph R., Bogard, Gwendolyn, Qiu, Jie, Dembowski, Mateusz, Burns, Peter C., & Casey, William H. Cation-Directed Isomerization of the U28 Uranyl-Peroxide Cluster: Cation-Directed Isomerization of the U28 Uranyl-Peroxide Cluster. United States. doi:10.1002/ejic.201701074.
Oliveri, Anna F., Colla, Christopher A., Callahan, Joseph R., Bogard, Gwendolyn, Qiu, Jie, Dembowski, Mateusz, Burns, Peter C., and Casey, William H. Thu . "Cation-Directed Isomerization of the U28 Uranyl-Peroxide Cluster: Cation-Directed Isomerization of the U28 Uranyl-Peroxide Cluster". United States. doi:10.1002/ejic.201701074. https://www.osti.gov/servlets/purl/1470042.
@article{osti_1470042,
title = {Cation-Directed Isomerization of the U28 Uranyl-Peroxide Cluster: Cation-Directed Isomerization of the U28 Uranyl-Peroxide Cluster},
author = {Oliveri, Anna F. and Colla, Christopher A. and Callahan, Joseph R. and Bogard, Gwendolyn and Qiu, Jie and Dembowski, Mateusz and Burns, Peter C. and Casey, William H.},
abstractNote = {The conformational dynamics of nanometer-sized actinide ions are exceptionally sensitive to the choice of counter-cations. A new means of following these dynamics in solution is presented that follows 1H NMR signals. The direct bond between hydrogen and phosphorus atoms in the bridging phosphonic groups of the [(UO2)28(O2)20(PHO3)24(H2O)12]32– (U28) cluster allows unparalleled recording of the orientations of these bridges in situ. The µ3-PHO3 bridges are organized into two supersets of conformers (facing inward vs. outward from the cluster), but each of these supersets additionally have four subsets that can be identified based upon orientations of the lone pairs of electrons in the associated oxygen atoms. The ensemble of these subsets changes over days or weeks depending upon bulk solution chemistry, temperature, and pressure. They also reflect cations trapped within the molecule. The 1H NMR spectra at room temperature indicate that the molecular orientation of this enormous ion tunes itself in response to solution composition, which suggests a strategy for selecting host–guest combinations.},
doi = {10.1002/ejic.201701074},
journal = {European Journal of Inorganic Chemistry},
number = [46],
volume = [2017],
place = {United States},
year = {2017},
month = {9}
}

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From extended solids to nano-scale actinide clusters
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Studtite, [(UO 2 )(O 2 )(H 2 O) 2 ](H 2 O) 2 : The first structure of a peroxide mineral
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    Works referencing / citing this record:

    Hybrid Uranium-Oxalate Fullerene Topology Cage Clusters
    journal, August 2010

    • Ling, Jie; Wallace, Christine M.; Szymanowski, Jennifer E. S.
    • Angewandte Chemie, Vol. 122, Issue 40
    • DOI: 10.1002/ange.201003197

    Hybrid Uranium-Oxalate Fullerene Topology Cage Clusters
    journal, August 2010

    • Ling, Jie; Wallace, Christine M.; Szymanowski, Jennifer E. S.
    • Angewandte Chemie International Edition, Vol. 49, Issue 40
    • DOI: 10.1002/anie.201003197

    Dynamic Phosphonic Bridges in Aqueous Uranyl Clusters
    journal, February 2016

    • Oliveri, Anna F.; Pilgrim, Corey D.; Qiu, Jie
    • European Journal of Inorganic Chemistry, Vol. 2016, Issue 6
    • DOI: 10.1002/ejic.201600036

    From extended solids to nano-scale actinide clusters
    journal, June 2010


    Nuclear Archeology in a Bottle: Evidence of Pre-Trinity U.S. Weapons Activities from a Waste Burial Site
    journal, February 2009

    • Schwantes, Jon M.; Douglas, Matthew; Bonde, Steven E.
    • Analytical Chemistry, Vol. 81, Issue 4
    • DOI: 10.1021/ac802286a

    Clusters of Actinides with Oxide, Peroxide, or Hydroxide Bridges
    journal, October 2012

    • Qiu, Jie; Burns, Peter C.
    • Chemical Reviews, Vol. 113, Issue 2
    • DOI: 10.1021/cr300159x

    Characterization of High Phosphate Radioactive Tank Waste and Simulant Development
    journal, October 2009

    • Lumetta, Gregg J.; McNamara, Bruce K.; Buck, Edgar C.
    • Environmental Science & Technology, Vol. 43, Issue 20
    • DOI: 10.1021/es9013745

    Time-Resolved Assembly of Chiral Uranyl Peroxo Cage Clusters Containing Belts of Polyhedra
    journal, December 2012

    • Qiu, Jie; Nguyen, Kevin; Jouffret, Laurent
    • Inorganic Chemistry, Vol. 52, Issue 1
    • DOI: 10.1021/ic3020817

    Time-Resolved Self-Assembly of a Fullerene-Topology Core–Shell Cluster Containing 68 Uranyl Polyhedra
    journal, January 2012

    • Qiu, Jie; Ling, Jie; Sui, Audrey
    • Journal of the American Chemical Society, Vol. 134, Issue 3
    • DOI: 10.1021/ja210163b

    Uranyl−Peroxide Interactions Favor Nanocluster Self-Assembly
    journal, November 2009

    • Sigmon, Ginger E.; Ling, Jie; Unruh, Daniel K.
    • Journal of the American Chemical Society, Vol. 131, Issue 46
    • DOI: 10.1021/ja907837u

    Changes in the Si−O Vibrations of Smectite Layers Accompanying the Sorption of Interlayer Water
    journal, January 1996

    • Yan, Laibin; Roth, Charles B.; Low, Philip F.
    • Langmuir, Vol. 12, Issue 18
    • DOI: 10.1021/la960119e

    Mechanism of decomposition of water by ionizing radiations
    journal, January 1952


    Effects of exchangeable cations on the adsorption properties of Na+ mordenite
    journal, January 1991

    • Tyburce, Bernard; Kappenstein, Charles; Cartraud, Pierre
    • Journal of the Chemical Society, Faraday Transactions, Vol. 87, Issue 17
    • DOI: 10.1039/ft9918702849

    Stability of Peroxide-Containing Uranyl Minerals
    journal, November 2003


    Nanoscale uranium-based cage clusters inspired by uranium mineralogy
    journal, February 2011


    Studtite, [(UO 2 )(O 2 )(H 2 O) 2 ](H 2 O) 2 : The first structure of a peroxide mineral
    journal, July 2003

    • Burns, Peter C.; Hughes, Karrie-Ann
    • American Mineralogist, Vol. 88, Issue 7
    • DOI: 10.2138/am-2003-0725