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

Journal Article · · European Journal of Inorganic Chemistry
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
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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 1 H 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 2 O) 12 ] 32– ( U 28 ) 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 1 H 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.

Research Organization:
Energy Frontier Research Centers (EFRC) (United States). Materials Science of Actinides (MSA)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
SC0001089; DE‐SC0001089
OSTI ID:
1470042
Alternate ID(s):
OSTI ID: 1398815
Journal Information:
European Journal of Inorganic Chemistry, Vol. 2017, 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; ISSN 1434-1948
Publisher:
ChemPubSoc EuropeCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 1 work
Citation information provided by
Web of Science

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
nuclear (including radiation effects)
materials and chemistry by design
synthesis (novel materials)
synthesis (self-assembly)