Smetana Volodymyr, Bolla Geetha, Hiti Ethan A, Wineinger Hannah, Mudring Anja-Verena, Rogers Robin D
Department of Biological and Chemical Engineering and iNANO, Aarhus University, 8000 Aarhus C, Denmark.
Department of Chemistry, University of Wyoming, 1000 E, University Ave, Laramie, Wyoming 82071, United States.
Cryst Growth Des. 2025 Jul 19;25(15):6421-6428. doi: 10.1021/acs.cgd.5c00835. eCollection 2025 Aug 6.
Reactions of lanthanide-(III) chloride salts with 4-amino-1,2,4-triazole (4-NH-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 [NdCl(μ-4-NH-1,2,4-Triaz)(4-NH-1,2,4-Triaz)], [CeCl(μ-Cl)(μ-4-NH-1,2,4-Triaz)], [Ce(μ-Cl)(μ-OH)(μ-4-NH-1,2,4-Triaz)], [LnCl(μ-Cl)(μ-OH)(μ-4-NH-1,2,4-Triaz)]·2HO (Ln = Ce, Nd), and [CeCl(μ-O)-(μ-Cl)(μ-Cl)(μ-OH)(μ-4-NH-1,2,4-Triaz)((OH))][CeCl]-[Cl]·HO. In all complexes, all lanthanide atoms are pairwise connected via one or more 4-NH-1,2,4-Triaz ligands and sometimes additional Cl anions.
镧系（III）氯化物盐与4-氨基-1,2,4-三唑（4-NH-1,2,4-Triaz）在唑类熔体中的反应，使得在同一合成过程中既分离出了水解产物，也分离出了非水解产物，其中包含多种配体、阴离子和水，这使我们能够捕捉到不同形式和中间水解片段的晶体学快照。本文报道的结构研究包括无水和水合的非水解配合物，它们与水解产物一起被分离出来，得到了氧化物/氢氧化物镧系（III）二聚体、四聚体，最终还有六聚体。分离出的化合物包括[NdCl(μ-4-NH-1,2,4-Triaz)(4-NH-1,2,4-Triaz)]、[CeCl(μ-Cl)(μ-4-NH-1,2,4-Triaz)]、[Ce(μ-Cl)(μ-OH)(μ-4-NH-1,2,4-Triaz)]、[LnCl(μ-Cl)(μ-OH)(μ-4-NH-1,2,4-Triaz)]·2H₂O（Ln = Ce，Nd）以及[CeCl(μ-O)-(μ-Cl)(μ-Cl)(μ-OH)(μ-4-NH-1,2,4-Triaz)((OH))][CeCl]-[Cl]·H₂O。在所有配合物中，所有镧系原子通过一个或多个4-NH-1,2,4-Triaz配体以及有时额外的Cl⁻阴离子成对连接。
