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Title: Solution and Solid State Structural Chemistry of Th(IV) and U(IV) 4-Hydroxybenzoates

Journal Article · · Inorganic Chemistry
 [1];  [1];  [1];  [2];  [2]; ORCiD logo [3]; ORCiD logo [1];  [4]; ORCiD logo [3]; ORCiD logo [2]; ORCiD logo [1]
  1. Georgetown Univ., Washington, DC (United States). Dept. of Chemistry
  2. Oregon State Univ., Corvallis, OR (United States). Dept. of Chemistry
  3. Univ. of Pennsylvania, Philadelphia, PA (United States). P. Roy and Diana T. Vagelos Lab. and Dept. of Chemistry
  4. Georgetown Univ., Washington, DC (United States). Dept. of Physics
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Organic ligands with carboxylate functionalities have been shown to affect the solubility, speciation, and overall chemical behavior of tetravalent metal ions. While many reports have focused on actinide complexation by relatively simple monocarboxylates such as amino acids, here we examined Th(IV) and U(IV) complexation by 4-hydroxybenzoic acid in water with the aim of understanding the impact that the organic backbone has on the solution and solid state structural chemistry of thorium(IV) and uranium(IV) complexes. Two compounds of the general formula [An6O4(OH)4(H2O)6(4-HB)12]·nH2O [An = Th (Th-1) and U (U-1); 4-HB = 4-hydroxybenzoate] were synthesized via roomtemperature reactions of AnCl4 and 4-hydroxybenzoic acid in water. Solid state structures were determined by single-crystal X-ray diffraction, and the compounds were further characterized by Raman, infrared, and optical spectroscopies and thermogravimetry. The magnetism of U-1 was also examined. The structures of the Th and U compounds are isomorphous and are built from ligand-decorated oxo/hydroxo-bridged hexanuclear units. The relationship between the building units observed in the solid state structure of U-1 and those that exist in solution prior to crystallization as well as upon dissolution of U-1 in nonaqueous solvents was investigated using small-angle X-ray scattering, ultraviolet-visible optical spectroscopy, and dynamic light scattering. The evolution of U solution speciation as a function of reaction time and temperature was examined. Such effects as well as the impact of the ligand on the formation and evolution of hexanuclear U(IV) clusters to UO2 nanoparticles compared to prior reported monocarboxylate ligand systems are discussed. Unlike prior reported syntheses of Th and U(IV) hexamers where the pH was adjusted to ~2 and 3, respectively, to drive hydrolysis, hexamer formation with the HB ligand appears to be promoted only by the ligand.

Research Organization:
Oregon State Univ., Corvallis, OR (United States)
Sponsoring Organization:
USDOE National Nuclear Security Administration (NNSA); USDOE Office of Science (SC), Basic Energy Sciences (BES); Henry Luce Foundation. Clare Boothe Luce (CBL) Program; National Science Foundation (NSF)
Grant/Contract Number:
NA0003763; SC0017259; CHE-1429079; CHE-1337975
OSTI ID:
1468988
Journal Information:
Inorganic Chemistry, Vol. 57, Issue 12; ISSN 0020-1669
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 27 works
Citation information provided by
Web of Science

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Cited By (9)

From Isolated Molecular Complexes to Extended Networks: Synthesis and Characterization of Thorium Furanmono- and Dicarboxylates: From Isolated Molecular Complexes to Extended Networks: Synthesis and Characterization of Thorium Furanmono- and Dicarboxylates journal July 2020
Titanium phosphonate oxo-alkoxide “clusters”: solution stability and facile hydrolytic transformation into nano titania journal January 2020
Structural Snapshots of Cluster Growth from {U 6 } to {U 38 } During the Hydrolysis of UCl 4 journal January 2019
On the Aqueous Chemistry of the U IV –DOTA Complex journal March 2020
Tetranuclear oxido-bridged thorium( iv ) clusters obtained using tridentate Schiff bases journal January 2019
Structural Snapshots of Cluster Growth from {U 6 } to {U 38 } During the Hydrolysis of UCl 4 journal January 2019
Time-controlled synthesis of the 3D coordination polymer U(1,2,3-Hbtc) 2 followed by the formation of molecular poly-oxo cluster {U 14 } containing hemimellitate uranium( iv ) journal January 2019
Mononuclear to Polynuclear U IV Structural Units: Effects of Reaction Conditions on U‐Furoate Phase Formation journal April 2020
Bridging the Transuranics with Uranium(IV) Sulfate Aqueous Species and Solid Phases journal November 2020

Linked Research (2)

Figures / Tables (9)

Table 1(p. 8)table Table 1
Figure 1(p. 14)figure Figure 1
Figure 2(p. 18)figure Figure 2
Figure 3(p. 19)figure Figure 3
Figure 4(p. 21)figure Figure 4
Figure 5(p. 22)figure Figure 5
Figure 6(p. 24)figure Figure 6
Figure 7(p. 25)figure Figure 7
Figure 8(p. 27)figure Figure 8

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