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Title: Cation-Directed Isomerization of the U28 Uranyl-Peroxide Cluster: Cation-Directed Isomerization of the U28 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 [(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.

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)
OSTI Identifier:
1470042
Alternate Identifier(s):
OSTI ID: 1398815
Grant/Contract Number:  
SC0001089; DE‐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. https://doi.org/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. https://doi.org/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. https://doi.org/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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