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Title: Solution 31P NMR Study of the Acid-Catalyzed Formation of a Highly Charged {U24Pp12} Nanocluster, [(UO2)24(O2) 24(P2O7)12]48–, and Its Structural Characterization in the Solid State Using Single-Crystal Neutron Diffraction

Abstract

The first neutron diffraction study of a single crystal containing uranyl peroxide nanoclusters is reported herein for pyrophosphate-functionalized Na44K6[(UO2)24(O2)24(P2O7)12][IO3]2·140H2O (1). Relative to earlier X-ray studies, neutron diffraction provides superior information concerning the positions of H atoms and lighter counterions. Hydrogen positions have been assigned and reveal an extensive network of H-bonds; notably, most O atoms present in the anionic cluster accept H-bonds from surrounding H2O molecules, and none of the surface-bound O atoms are protonated. The D4h symmetry of the cage is consistent with the presence of six encapsulated K cations, which appear to stabilize the lower symmetry variant of this cluster. 31P NMR measurements demonstrate retention of this symmetry in solution, while in situ 31P NMR studies suggest an acid-catalyzed mechanism for the assembly of 1 across a wide range of pH values.

Authors:
 [1];  [1];  [1];  [2];  [2];  [1];  [2];  [1];  [1]
+ Show Author Affiliations
  1. Univ. of Notre Dame, IN (United States)
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Materials Science of Actinides (MSA); Univ. of Notre Dame, IN (United States); Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Spallation Neutron Source (SNS)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities Division
OSTI Identifier:
1387908
Grant/Contract Number:  
SC0001089; AC05-00OR22725
Resource Type:
Accepted Manuscript
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Volume: 138; Journal Issue: 27; 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 0002-7863
Publisher:
American Chemical Society (ACS)
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); oxygen; oxides; anions; cluster chemistry; cations

Citation Formats

Dembowski, Mateusz, Olds, Travis A., Pellegrini, Kristi L., Hoffmann, Christina, Wang, Xiaoping, Hickam, Sarah, He, Junhong, Oliver, Allen G., and Burns, Peter C.. Solution 31P NMR Study of the Acid-Catalyzed Formation of a Highly Charged {U24Pp12} Nanocluster, [(UO2)24(O2) 24(P2O7)12]48–, and Its Structural Characterization in the Solid State Using Single-Crystal Neutron Diffraction. United States: N. p., 2016. Web. doi:10.1021/jacs.6b04028.
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Dembowski, Mateusz, Olds, Travis A., Pellegrini, Kristi L., Hoffmann, Christina, Wang, Xiaoping, Hickam, Sarah, He, Junhong, Oliver, Allen G., & Burns, Peter C.. Solution 31P NMR Study of the Acid-Catalyzed Formation of a Highly Charged {U24Pp12} Nanocluster, [(UO2)24(O2) 24(P2O7)12]48–, and Its Structural Characterization in the Solid State Using Single-Crystal Neutron Diffraction. United States. https://doi.org/10.1021/jacs.6b04028
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Dembowski, Mateusz, Olds, Travis A., Pellegrini, Kristi L., Hoffmann, Christina, Wang, Xiaoping, Hickam, Sarah, He, Junhong, Oliver, Allen G., and Burns, Peter C.. Mon . "Solution 31P NMR Study of the Acid-Catalyzed Formation of a Highly Charged {U24Pp12} Nanocluster, [(UO2)24(O2) 24(P2O7)12]48–, and Its Structural Characterization in the Solid State Using Single-Crystal Neutron Diffraction". United States. https://doi.org/10.1021/jacs.6b04028. https://www.osti.gov/servlets/purl/1387908.
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@article{osti_1387908,
title = {Solution 31P NMR Study of the Acid-Catalyzed Formation of a Highly Charged {U24Pp12} Nanocluster, [(UO2)24(O2) 24(P2O7)12]48–, and Its Structural Characterization in the Solid State Using Single-Crystal Neutron Diffraction},
author = {Dembowski, Mateusz and Olds, Travis A. and Pellegrini, Kristi L. and Hoffmann, Christina and Wang, Xiaoping and Hickam, Sarah and He, Junhong and Oliver, Allen G. and Burns, Peter C.},
abstractNote = {The first neutron diffraction study of a single crystal containing uranyl peroxide nanoclusters is reported herein for pyrophosphate-functionalized Na44K6[(UO2)24(O2)24(P2O7)12][IO3]2·140H2O (1). Relative to earlier X-ray studies, neutron diffraction provides superior information concerning the positions of H atoms and lighter counterions. Hydrogen positions have been assigned and reveal an extensive network of H-bonds; notably, most O atoms present in the anionic cluster accept H-bonds from surrounding H2O molecules, and none of the surface-bound O atoms are protonated. The D4h symmetry of the cage is consistent with the presence of six encapsulated K cations, which appear to stabilize the lower symmetry variant of this cluster. 31P NMR measurements demonstrate retention of this symmetry in solution, while in situ 31P NMR studies suggest an acid-catalyzed mechanism for the assembly of 1 across a wide range of pH values.},
doi = {10.1021/jacs.6b04028},
journal = {Journal of the American Chemical Society},
number = 27,
volume = 138,
place = {United States},
year = {2016},
month = {6}
}
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https://doi.org/10.1021/jacs.6b04028
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Cited by: 27 works
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Figures / Tables:

Figure 1 Figure 1: Graphical (a) and polyhedral (b) representations of the cluster in the mixed Na and K salt of {U24Pp12}. Ball-and-stick representation of the {U4} unit (c) and bis-bidentate pyrophosphate bridges. U, P, and O atoms are shown as yellow, purple, and red spheres, respectively. In (a), lines represent linkagesmore » between polyhedra.« less
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    Works referencing / citing this record:

    Neutron Instruments for Research in Coordination Chemistry: Neutron Instruments for Research in Coordination Chemistry
    journal, January 2019

    • Xue, Zi-Ling; Ramirez-Cuesta, Anibal J.; Brown, Craig M.
    • European Journal of Inorganic Chemistry, Vol. 2019, Issue 8
    • DOI: 10.1002/ejic.201801076

    An unprecedented nanocage-like and heterometallic [MoIV3O 4 ]-polyoxomolybdate hybrid
    journal, January 2018

    • Xu, Xian; Luo, Ben-long; Wang, Lu-Lu
    • Dalton Transactions, Vol. 47, Issue 10
    • DOI: 10.1039/c7dt04309k

    Evidence for non-electrostatic interactions between a pyrophosphate-functionalized uranyl peroxide nanocluster and iron (hydr)oxide minerals
    journal, January 2019

    • Sadergaski, Luke R.; Perry, Samuel N.; Tholen, Luke R.
    • Environmental Science: Processes & Impacts, Vol. 21, Issue 7
    • DOI: 10.1039/c9em00139e
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