Crystallographic Snapshots of Pre- and Post-Lanthanide Halide Hydrolysis─Reaction Products Captured by the 4-Amino-1,2,4-triazole Ligand

Smetana, Volodymyr; Bolla, Geetha; Hiti, Ethan A.; Wineinger, Hannah; Mudring, Anja-Verena; Rogers, Robin D.

doi:10.1021/acs.cgd.5c00835

Crystallographic Snapshots of Pre- and Post-Lanthanide Halide Hydrolysis─Reaction Products Captured by the 4-Amino-1,2,4-triazole Ligand

Journal Article · Sat Jul 19 00:00:00 EDT 2025 · Crystal Growth and Design

DOI:https://doi.org/10.1021/acs.cgd.5c00835· OSTI ID:2587035

^[1]; ^[2]; ^[3]; Wineinger, Hannah ^[3]; ^[4]; ^[2]

Aarhus University (Denmark)
University of Wyoming, Laramie, WY (United States); The University of Alabama, Tuscaloosa, AL (United States)
The University of Alabama, Tuscaloosa, AL (United States)
Aarhus University (Denmark); Umeå University (Sweden)

Reactions of lanthanide(III) chloride salts with 4-amino-1,2,4-triazole (4-NH₂-1,2,4-Triaz) in azole melts have led to the isolation of both hydrolysis and nonhydrolysis products in the same synthesis, with the inclusion of a variety of ligands, anions, and water, allowing us to capture crystallographic snapshots of different forms and intermediate hydrolysis fragments. The structural studies reported here include anhydrous and hydrated nonhydrolyzed complexes, which were isolated alongside hydrolysis products, giving oxide/hydroxide lanthanide(III) dimers, tetramers, and ultimately hexamers. The compounds isolated include [Nd₂Cl₆(μ₂-4-NH₂-1,2,4-Triaz)₄(4-NH₂-1,2,4-Triaz)₂], [Ce₂Cl₄(μ₂-Cl)₂(μ₂-4-NH₂-1,2,4-Triaz)₄]_n, [Ce₂(μ₂-Cl)₄(μ₂-OH)₂(μ₂-4-NH₂-1,2,4-Triaz)₂]_n, [Ln₄Cl₄(μ₂-Cl)₄(μ₃-OH)₄(μ₂-4-NH₂-1,2,4-Triaz)₄]_n·2nH₂O (Ln = Ce, Nd), and [Ce₆Cl₆(μ₆-O_0.5)(μ₃-Cl_0.5)₄(μ₃-Cl_0.75)₃(μ₃-OH)_0.75(μ₂-4-NH₂-1,2,4-Triaz)₁₂((OH₂)_0.25)₂]₂[CeCl₆][Cl₉]·xH₂O. In all complexes, all lanthanide atoms are pairwise connected via one or more 4-NH₂-1,2,4-Triaz ligands and sometimes additional Cl^– anions.

View Accepted Manuscript (DOE)

Research Organization:: University of Wyoming, Laramie, WY (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); National Institutes of Health (NIH); National Science Foundation (NSF MRI); Novonordisk Foundation

Grant/Contract Number:: SC0025303

OSTI ID:: 2587035

Journal Information:: Crystal Growth and Design, Journal Name: Crystal Growth and Design Journal Issue: 15 Vol. 25; ISSN 1528-7505; ISSN 1528-7483

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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