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Title: Solution 31 P NMR Study of the Acid-Catalyzed Formation of a Highly Charged {U 24 Pp 12 } Nanocluster, [(UO 2 ) 24 (O 2 ) 24 (P 2 O 7 ) 12 ] 48– , and Its Structural Characterization in the Solid State Using Single-Crystal Neutron Diffraction

Authors:
 [1];  [2];  [2];  [3];  [3];  [2];  [4];  [1];  [5]
  1. Department of Chemistry and Biochemistry, University of Notre Dame, Notre Dame, Indiana 46556, United States
  2. Department of Civil and Environmental Engineering and Earth Sciences, University of Notre Dame, Notre Dame, Indiana 46556, United States
  3. Chemical and Engineering Materials Division, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831, United States
  4. Instrument and Source Division, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831, United States
  5. Department of Chemistry and Biochemistry, University of Notre Dame, Notre Dame, Indiana 46556, United States; Department of Civil and Environmental Engineering and Earth Sciences, University of Notre Dame, Notre Dame, Indiana 46556, United States
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:
1387908
DOE Contract Number:
SC0001089
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of the American Chemical Society; 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
Country of Publication:
United States
Language:
English
Subject:
nuclear (including radiation effects), materials and chemistry by design, synthesis (novel materials), synthesis (self-assembly)

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 31 P NMR Study of the Acid-Catalyzed Formation of a Highly Charged {U 24 Pp 12 } Nanocluster, [(UO 2 ) 24 (O 2 ) 24 (P 2 O 7 ) 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.
Dembowski, Mateusz, Olds, Travis A., Pellegrini, Kristi L., Hoffmann, Christina, Wang, Xiaoping, Hickam, Sarah, He, Junhong, Oliver, Allen G., & Burns, Peter C. Solution 31 P NMR Study of the Acid-Catalyzed Formation of a Highly Charged {U 24 Pp 12 } Nanocluster, [(UO 2 ) 24 (O 2 ) 24 (P 2 O 7 ) 12 ] 48– , and Its Structural Characterization in the Solid State Using Single-Crystal Neutron Diffraction. United States. doi:10.1021/jacs.6b04028.
Dembowski, Mateusz, Olds, Travis A., Pellegrini, Kristi L., Hoffmann, Christina, Wang, Xiaoping, Hickam, Sarah, He, Junhong, Oliver, Allen G., and Burns, Peter C. Tue . "Solution 31 P NMR Study of the Acid-Catalyzed Formation of a Highly Charged {U 24 Pp 12 } Nanocluster, [(UO 2 ) 24 (O 2 ) 24 (P 2 O 7 ) 12 ] 48– , and Its Structural Characterization in the Solid State Using Single-Crystal Neutron Diffraction". United States. doi:10.1021/jacs.6b04028.
@article{osti_1387908,
title = {Solution 31 P NMR Study of the Acid-Catalyzed Formation of a Highly Charged {U 24 Pp 12 } Nanocluster, [(UO 2 ) 24 (O 2 ) 24 (P 2 O 7 ) 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 = {},
doi = {10.1021/jacs.6b04028},
journal = {Journal of the American Chemical Society},
number = 27,
volume = 138,
place = {United States},
year = {Tue Jun 28 00:00:00 EDT 2016},
month = {Tue Jun 28 00:00:00 EDT 2016}
}
  • Single crystals of the new compounds Li{sub 6}[(UO{sub 2}){sub 12}(PO{sub 4}){sub 8}(P{sub 4}O{sub 13})] (1), Li{sub 5}[(UO{sub 2}){sub 13}(AsO{sub 4}){sub 9}(As{sub 2}O{sub 7})] (2), Li[(UO{sub 2}){sub 4}(AsO{sub 4}){sub 3}] (3) and Li{sub 3}[(UO{sub 2}){sub 7}(AsO{sub 4}){sub 5}O)] (4) have been prepared using high-temperature solid state reactions. The crystal structures have been solved by direct methods: 1-monoclinic, C2/m, a=26.963(3) A, b=7.063(1) A, c=19.639(1) A, beta=126.890(4){sup o}, V=2991.2(6) A{sup 3}, Z=2, R{sub 1}=0.0357 for 3248 unique reflections with |F{sub 0}|>=4sigma{sub F}; 2-triclinic, P1-bar, a=7.1410(8) A, b=13.959(1) A, c=31.925(1) A, alpha=82.850(2){sup o}, beta=88.691(2){sup o}, gamma=79.774(3){sup o}, V=3107.4(4) A{sup 3}, Z=2, R{sub 1}=0.0722 formore » 9161 unique reflections with |F{sub 0}|>=4sigma{sub F}; 3-tetragonal, I4{sub 1}/amd, a=7.160(3) A, c=33.775(9) A, V=1732(1) A{sup 3}, Z=4, R{sub 1}=0.0356 for 318 unique reflections with |F{sub 0}|>=4sigma{sub F}; 4-tetragonal, P4-bar, a=7.2160(5) A, c=14.6540(7) A, V=763.04(8) A{sup 3}, Z=1, R{sub 1}=0.0423 for 1600 unique reflections with |F{sub 0}|>=4sigma{sub F}. Structures of all the phases under consideration are based on complex 3D frameworks consisting of different types of uranium polyhedra (UO{sub 6} and UO{sub 7}) and different types of tetrahedral TO{sub 4} anions (T=P or As): PO{sub 4} and P{sub 4}O{sub 13} in 1, AsO{sub 4} and As{sub 2}O{sub 7} in 2, and single AsO{sub 4} tetrahedra in 3 and 4. In the structures of 1 and 2, UO{sub 7} pentagonal bipyramids share edges to form (UO{sub 5}){sub i}nfinity chains extended along the b axis in 1 and along the a axis in 2. The chains are linked via single TO{sub 4} tetrahedra into tubular units with external diameters of 11 A in 1 and 11.5 A in 2, and internal diameters of 4.1 A in 1 and 4.5 A in 2. The channels accommodate Li{sup +} cations. The tubular units are linked into 3D frameworks by intertubular complexes. Structures of 3 and 4 are based on 3D frameworks composed on layers united by (UO{sub 5}){sub i}nfinity infinite chains. Cation-cation interactions are observed in 2, 3, and 4. In 2, the structure contains a trimeric unit with composition [O=U(1)=O]-U(13)-[O=U(2)=O]. In the structures of 3 and 4, T-shaped dimers are observed. In all the structures, Li{sup +} cations are located in different types of cages and channels and compensate negative charges of anionic 3D frameworks. - Graphical abstract: The crystal structures of Li{sub 5}[(UO{sub 2}){sub 13}(AsO{sub 4}){sub 9}(As{sub 2}O{sub 7})] separated into tubular units and intertubular complexes.« less
  • The authors have investigated the mechanism and determined the enthalpy of crystallization of x-ray amorphous iron garnets of rare-earth elements and their solid solutions. The authors have established a relation between the mechanism of the solid-phase reaction of formation of the iron garnets and the decrease in the ionic radius of the rare-earth element in the dodecahedral positions. A rise in the temperature during crystallization of amorphous phases facilitates a rapid completion of the reaction in which double oxides with a complex three-sublattice structure are released.
  • The three new framework Rb uranyl phosphates and arsenates with anionic parts based on different type of polymeric anions have been prepared by high-temperature solid-state reactions: Rb{sub 4}[(UO{sub 2}){sub 6}(P{sub 2}O{sub 7}){sub 4}(H{sub 2}O)] (1), Rb{sub 2}[(UO{sub 2}){sub 3}(P{sub 2}O{sub 7})(P{sub 4}O{sub 12})] (2), Rb[(UO{sub 2}){sub 2}(As{sub 3}O{sub 10})] (3). The crystal structures of the synthesized compounds have been solved by direct methods: 1-monoclinic P2{sub 1}/c, a=9.672(1) A, b=12.951(1) A, c=32.231(3) A, beta=90.116(4){sup o}, V=4037.3(6) A{sup 3}, Z=4, R{sub 1}=0.0926 for 6351 unique reflections with |F{sub 0}|>=4sigma{sub F}; 2-monoclinic, P2{sub 1}/c, a=6.791(1) A, b=16.155(3) A, c=19.856(4) A, beta=97.48(5){sup o}, V=2159.8(7)more » A{sup 3}, Z=4, R{sub 1}=0.0286 for 3617 unique reflections with |F{sub 0}|>=4sigma{sub F}; 3-orthorhombic, Pbcn, a=10.558(1) A, b=11.037(1) A, c=11.464(1) A, V=1335.9(2) A{sup 3}, Z=4, R{sub 1}=0.0489 for 1384 unique reflections with |F{sub 0}|>=4sigma{sub F}. The structures of title are compounds based on 3D negatively charged frameworks with chemical compositions [(UO{sub 2}){sub 6}(P{sub 2}O{sub 7}){sub 4}(H{sub 2}O)]{sup 4-} in 1, [(UO{sub 2}){sub 3}(P{sub 2}O{sub 7})(P{sub 4}O{sub 12})]{sup 2-} in 2 and [(UO{sub 2}){sub 2}(As{sub 3}O{sub 10})]{sup -} in 3. These negative charges are compensated by rubidium cations which are in the channels of 1 and closed cages in structures of 2 and 3. The channels in 1 are directed along the a direction and have minimum dimensions approx5 Ax6 A. This is the first example of porosity generation through solid state synthesis in uranyl compounds. For the first time in uranium chemistry polymeric anionic groups P{sub 4}O{sub 12} and As{sub 3}O{sub 10} were observed in structure of 2 and 3. - Graphical abstract: The polyhedral (a) and topological (b) representation of the Rb{sub 4}[(UO{sub 2}){sub 6}(P{sub 2}O{sub 7}){sub 4}(H{sub 2}O)] crystal structure.« less
  • Trace amounts of H/sub 2/O and limited exposure to air of reaction mixtures of UCl/sub 4/ and 12-crown-4, 15-crown-5, benzo-15-crown-5, 18-crown-6, or dibenzo-18-crown-6 in 1:3 mixtures of CH/sub 3/OH and CH/sub 3/CN resulted in the hydrolysis and oxidation of UCl/sub 4/ to (UO/sub 2/Cl/sub 4/)/sup 2/minus//. In the presence of these crown ethers, it has been possible to isolate intermediate products via crystallization of crown complexes of the (UO/sub 2/Cl/sub 4/)/sup 2/minus// ion, the (UCl/sub 6/)/sup 2/minus// ion, and (UO/sub 2/Cl/sub 2/(OH/sub 2/)/sub 3/). The neutral moiety crystallizes as a hydrogen-bonded crown ether complex; however, crown ether complexation of amore » counterion, either an ammonium ion formed during the oxidation of U(IV) or a Na/sup +/ ion leached from glass reaction vessels, resulted in novel crystalline complexes of the ionic species. ((NH/sub 4/)(15-crown-5)/sub 2/)/sub 2/(UO/sub 2/Cl/sub 4/) /times/ 2CH/sub 3/CN, ((NH/sub 4/)(benzo-15-crown-5)/sub 2/)/sub 2/(UCl/sub 6/) /times/ 4CH/sub 3/CN, and ((NH/sub 4/)(dibenzo-18-crown-6))/sub 2/(UO/sub 2/Cl/sub 4/) /times/ 2CH/sub 3/CN have been structurally characterized by single-crystal X-ray diffraction techniques. The results of all the crystal studies are presented in detail. The ammonium ions interact with the crown ethers via hydrogen-bonding and electrostatic interactions. 15-Crown-5 and benzo-15-crown-5 form 2:1 sandwich cations, allowing no H/sub 4/N/sup +//hor ellipsis/(UO/sub 2/Cl/sub 4/)/sup 2/minus// interaction. The dibenzo-18-crown-6 complexed ammonium ions are 1:1 and form bifurcated hydrogen bonds with the chlorine atoms in the (UO/sub 2/Cl/sub 4/)/sup /minus// anion. The formation of (Na(12-crown-4)/sub 2//sub 2/(UO/sub 2/Cl/sub 4/) /times/ 2OHMe and (UO/sub 2/Cl/sub 2/(OH)/sub 2/)/sub 3/) /times/ 18-crown-6 /times/ H/sub 2/O /times/ OHMe has been confirmed by preliminary single-crystal X-ray diffraction studies.« less
  • Deuterium isotope effects on /sup 31/P shielding that are large relative to the accuracy with which they can be measured are reported. In (Ph/sub 3/P)/sub 2/IrH/sub 2/(dmf)/sub 2//sup +/, substitution of one /sub 2/H for one /sup 1/H at the Ir-H or at the ortho position in the Ph/sub 3/P ligand leads to two- and three-bond isotope shifts of +0.094 and /minus/0.110 ppm, respectively, with the effect being defined as (/delta/(/sup 2/Hf form) - /delta/(/sup 1/H form)). The ortho-deuterium effects on /sup 31/P for Ph/sub 3/P, Ph/sub 3/PO, Ph/sub 3/PMe/sup +/I/sup /minus//, and (Ph/sub 3/P)/sub 2/Ir(C/sub 8/H/sub 12/)/sup +/ aremore » /minus/0.110, /minus/0.096, /minus/0.035, and /minus/0.077 ppm, respectively. These long-range isotope effects are used to demonstrate a thermally activated, solid-state exchange of deuterium between iridium and only the ortho positions of the Ph/sub 3/P ligands in ((Ph/sub 3/P)/sub 2/IrH/sub 2/)/sub 3/PW/sub 12/O/sub 40/. There occurs, additionally, an intermolecular hydrogen-deuterium exchange process. Slow exchange with c-C/sub 6/D/sub 12/ leads to incorporation of the deuterium label in the Ph/sub 3/P rings.« less