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

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

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

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

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

3 Scopus citations

Abstract

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.

Original language	English
Pages (from-to)	6421-6428
Number of pages	8
Journal	Crystal Growth and Design
Volume	25
Issue number	15
DOIs	https://doi.org/10.1021/acs.cgd.5c00835
State	Published - 6 Aug 2025
Externally published	Yes

ASJC Scopus subject areas

General Chemistry
General Materials Science
Condensed Matter Physics

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10.1021/acs.cgd.5c00835

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@article{2239a0cd28fd4af7a7fd47eec06523cb,

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

abstract = "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-O0.5)(μ3-Cl0.5)4(μ3-Cl0.75)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{\textendash} anions.",

author = "Volodymyr Smetana and Geetha Bolla and Hiti, \{Ethan A.\} and Hannah Wineinger and Mudring, \{Anja Verena\} and Rogers, \{Robin D.\}",

note = "Publisher Copyright: {\textcopyright} 2025 The Authors. Published by American Chemical Society",

year = "2025",

month = aug,

day = "6",

doi = "10.1021/acs.cgd.5c00835",

language = "English",

volume = "25",

pages = "6421--6428",

journal = "Crystal Growth and Design",

issn = "1528-7483",

publisher = "American Chemical Society",

number = "15",

}

TY - JOUR

T1 - Crystallographic Snapshots of Pre- and Post-Lanthanide Halide Hydrolysis─Reaction Products Captured by the 4-Amino-1,2,4-triazole Ligand

AU - Smetana, Volodymyr

AU - Bolla, Geetha

AU - Hiti, Ethan A.

AU - Wineinger, Hannah

AU - Mudring, Anja Verena

AU - Rogers, Robin D.

PY - 2025/8/6

Y1 - 2025/8/6

N2 - 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-O0.5)(μ3-Cl0.5)4(μ3-Cl0.75)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.

AB - 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-O0.5)(μ3-Cl0.5)4(μ3-Cl0.75)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.

UR - https://www.scopus.com/pages/publications/105013038696

U2 - 10.1021/acs.cgd.5c00835

DO - 10.1021/acs.cgd.5c00835

M3 - Article

C2 - 40852389

AN - SCOPUS:105013038696

SN - 1528-7483

VL - 25

SP - 6421

EP - 6428

JO - Crystal Growth and Design

JF - Crystal Growth and Design

IS - 15

ER -

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

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