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Exploring the Role of Neutral 4-Amino-1,2,4-triazole in the Formation of Hexanuclear f-Element Hydrolysis Products

Journal Article · · Crystal Growth and Design
 [1];  [2];  [3];  [3];  [4]
  1. University of Alabama, Tuscaloosa, AL (United States); The University of Alabama
  2. University of Alabama, Tuscaloosa, AL (United States)
  3. Stockholm University (Sweden); Aarhus University (Denmark)
  4. University of Alabama, Tuscaloosa, AL (United States); Stockholm University (Sweden)
+ Show Author Affiliations

Our recent observations of an unexpected Ce(III) hydrolysis product from the reaction of 4-amino-1,2,4-triazole (4-NH2-1,2,4-Triaz) with CeCl3·7H2O, [Ce6(μ3-O)4(μ3-OH)2(μ3-Cl)2(Cl)6(μ2-4-NH2-1,2,4-Triaz)12]·7H2O, the first high-nuclearity lanthanide complex where all Ln atoms are connected pairwise through 12 N-donor ligands or 12 neutral bridging ligands of any type, prompted us to explore the utility of this ligand in trapping additional f-element examples. Reactions of LnCl3·6H2O (Ln = Nd, Eu, Ho) with a large excess of 4-NH2-1,2,4-Triaz (20 equiv) and with the addition of small amounts of water to help solubilize the metal salts led to the isolation of the unique hydrolysis products [Nd6(μ3-OH)8Cl6(μ2-4-NH2-1,2,4-Triaz)12][Cl4]·2H2O, [Eu6(μ6-Cl)0.23(μ3-O0.77)4(μ3-O)2.6(μ3-Cl)0.4Cl6(μ2-4-NH2-1,2,4-Triaz)12], and [Ho6(μ6-Cl)0.21(μ3-O0.79)4(μ3-OH)2Cl6(μ2-4-NH2-1,2,4-Triaz)12][Cl]3.4. Here, we also report a Ce(III) analogue prepared in glassware contaminated with Pb(OAc)2, namely, [Ce6(μ3-OH)8(BrPbBr5)(μ2-4-NH2-1,2,4-Triaz)11.5(OH2)6][Pb0.84Br4.2][Br]3.8·2(4-NH2-1,2,4-Triaz)·3.6H2O. The Nd(III) complex is the structurally most ordered with a clear [Nd6(μ3-OH)8] cluster core, while the Eu(III) and Ho(III) compounds contain partial occupancy of a μ6 position and thus result in an incomplete Ln6O9 cluster core formation. The crystallographic results suggest that the 4-NH2-1,2,4-Triaz ligand brings Ln(III) ions together, followed by the formation of an Ln6O8 or Ln6O9 core with whatever remaining anions or ligands can be incorporated. Given the complexity of the hydrolysis products of nuclear waste, we expect to continue to find a myriad of closely related complex structures of these types for the f-elements.

Research Organization:
University of Alabama, Tuscaloosa, AL (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
SC0019220
OSTI ID:
2371243
Journal Information:
Crystal Growth and Design, Journal Name: Crystal Growth and Design Journal Issue: 2 Vol. 24; ISSN 1528-7483
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English

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Related Subjects

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY
anions
azoles
cluster chemistry
crystal structure
f-elements
hydrolysis products
ligands
metals
nuclear waste