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

Mateusz Dembowski; Travis A. Olds; Kristi L. Pellegrini; Christina Hoffmann; Xiaoping Wang; Sarah Hickam; Junhong He; Allen G. Oliver; Peter C. Burns

doi:10.1021/jacs.6b04028

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

Mateusz Dembowski, Travis A. Olds, Kristi L. Pellegrini, Christina Hoffmann, Xiaoping Wang, Sarah Hickam, Junhong He, Allen G. Oliver, Peter C. Burns

Research output: Contribution to journal › Article › peer-review

32 Scopus citations

Abstract

The first neutron diffraction study of a single crystal containing uranyl peroxide nanoclusters is reported 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 D_4h 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.

Original language	English
Pages (from-to)	8547-8553
Number of pages	7
Journal	Journal of the American Chemical Society
Volume	138
Issue number	27
DOIs	https://doi.org/10.1021/jacs.6b04028
State	Published - Jul 13 2016

Bibliographical note

Publisher Copyright:
© 2016 American Chemical Society.

Funding

This material is based upon work supported as a part of the Materials Science of Actinides Center, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under Award No. DE-SC0001089. NMR measurements were conducted at the Magnetic Resonance Research Center at the University of Notre Dame. Electrospray ionization mass spectra were collected at the Mass Spectrometry and Proteomics Facility at University of Notre Dame. Raman spectroscopy and thermogravimetric analysis measurements were collected at the Materials Characterization Facility of the Center for Sustainable Energy at the University of Notre Dame. Work performed at the ORNL Spallation Neutron Source's TOPAZ single-crystal diffractometer was supported by the Scientific User Facilities Division, Office of Basic Energy Sciences, U.S. Department of Energy, under Contract No. DE-AC05- 00OR22725 with UT-Battelle, LLC.

Funders	Funder number
Scientific User Facilities Division	DE-AC05- 00OR22725
U.S. Department of Energy
Office of Science
Basic Energy Sciences	DE-SC0001089
Oak Ridge National Laboratory

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Dembowski, M., Olds, T. A., Pellegrini, K. L., Hoffmann, C., Wang, X., Hickam, S., He, J., Oliver, A. G., & Burns, P. C. (2016). 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. Journal of the American Chemical Society, 138(27), 8547-8553. https://doi.org/10.1021/jacs.6b04028

Dembowski, Mateusz ; Olds, Travis A. ; Pellegrini, Kristi L. et al. / 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. In: Journal of the American Chemical Society. 2016 ; Vol. 138, No. 27. pp. 8547-8553.

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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 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.",

author = "Mateusz Dembowski and Olds, {Travis A.} and Pellegrini, {Kristi L.} and Christina Hoffmann and Xiaoping Wang and Sarah Hickam and Junhong He and Oliver, {Allen G.} and Burns, {Peter C.}",

note = "Publisher Copyright: {\textcopyright} 2016 American Chemical Society.",

year = "2016",

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doi = "10.1021/jacs.6b04028",

language = "English",

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Dembowski, M, Olds, TA, Pellegrini, KL, Hoffmann, C , Wang, X, Hickam, S, He, J, Oliver, AG & Burns, PC 2016, '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', Journal of the American Chemical Society, vol. 138, no. 27, pp. 8547-8553. https://doi.org/10.1021/jacs.6b04028

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. / Dembowski, Mateusz; Olds, Travis A.; Pellegrini, Kristi L. et al.
In: Journal of the American Chemical Society, Vol. 138, No. 27, 13.07.2016, p. 8547-8553.

Research output: Contribution to journal › Article › peer-review

TY - JOUR

T1 - 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

AU - Dembowski, Mateusz

AU - Olds, Travis A.

AU - Pellegrini, Kristi L.

AU - Hoffmann, Christina

AU - Wang, Xiaoping

AU - Hickam, Sarah

AU - He, Junhong

AU - Oliver, Allen G.

AU - Burns, Peter C.

PY - 2016/7/13

Y1 - 2016/7/13

N2 - The first neutron diffraction study of a single crystal containing uranyl peroxide nanoclusters is reported 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.

AB - The first neutron diffraction study of a single crystal containing uranyl peroxide nanoclusters is reported 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.

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U2 - 10.1021/jacs.6b04028

DO - 10.1021/jacs.6b04028

M3 - Article

AN - SCOPUS:84978712575

SN - 0002-7863

VL - 138

SP - 8547

EP - 8553

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 27

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Dembowski M, Olds TA, Pellegrini KL, Hoffmann C , Wang X, Hickam S et al. 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. Journal of the American Chemical Society. 2016 Jul 13;138(27):8547-8553. doi: 10.1021/jacs.6b04028