Synthesis, Crystal Structure, and Properties of REE Nitrate Complexes with a Nitrosonium Cation

IF 1.4 4区化学 Q4 CHEMISTRY, INORGANIC & NUCLEAR

Journal of Structural Chemistry Pub Date : 2025-08-29 DOI:10.1134/S0022476625080141

A. A. Vorobyova, S. I. Troyanov, M. M. Baitemirov, G. D. Chistyakov, V. E. Goncharenko, A. A. Krainyukov, K. V. Zakharov, A. I. Boltalin, K. A. Lysenko, I. V. Morozov

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引用次数: 0

Abstract

Nitrate REE complexes with a nitrosonium cation (NO)₃[Ln₂(NO₃)₉] Ln = La (1), Ce (2), Eu (3), Gd (4), Tb (5), Dy (6)); (NO)₂[Ln(NO₃)₅], Ln = Er (8), Tm (9), Yb (10), Y (11); Na(NO)[Y(NO₃)₅] (12), Na(NO)[Y(NO₃)₅] (13), and NO[Ho(NO₃)₄] (14) are prepared by the crystallization from nitric-acid solutions and structurally characterized by XRD. Depending on the REE radius, the following different coordination polyhedra and types of structures can formed: 3D anionic framework with a [LnO₁₂] (Ln = La–Dy) icosahedral polyhedron; island structures with a [LnO₁₀] (Ln = Er–Y) tetradodecahedron, and 1D chains in the case of holmium with an environment responding to a bicapped tetragonal antiprism. In 1-14, NO⁺ participates in quite strong N⋯O and O⋯O interactions c nitrate groups. The influence of lanthanide compression on the geometry of complex polyhedra is discussed; features of NO⁺ coordination are considered. It is shown on the example of 3, 6, 10 that thermolysis leads to consecutive formation of anhydrous nitrates, LnONO₃ oxonitrates, and REE oxides. The magnetic susceptibility study of 8 revealed no noticeable deviations from paramagnetic behavior.

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含亚硝基离子的稀土硝酸盐配合物的合成、晶体结构和性能

硝酸盐稀土配合物与亚硝基离子（NO）3[Ln2(NO3)9] Ln = La (1), Ce (2), Eu (3), Gd (4), Tb (5), Dy (6))；(没有)2 (Ln(3号)5),Ln =呃(8),Tm (9), Yb (10), Y (11);采用硝酸溶液结晶法制备了Na(NO)[Y(NO3)5]（12）、Na(NO)[Y(NO3)5]（13）和NO[Ho(NO3)4](14)，并用XRD对其进行了结构表征。根据稀土元素半径的不同，可以形成以下不同的配位多面体和结构类型：具有[LnO12] （Ln = La-Dy）二十面体的三维阴离子框架；具有[LnO10] （Ln = Er-Y）四十二面体的岛状结构，以及具有二元反棱镜响应环境的钬的一维链。在1-14中，NO+参与了很强的N⋯O和O⋯O相互作用。讨论了镧系元素压缩对复杂多面体几何形状的影响；考虑了NO+配位的特征。在3,6,10的例子中，热裂解导致无水硝酸盐，LnONO3氧硝酸盐和REE氧化物的连续生成。磁化率研究显示8的顺磁行为没有明显的偏差。

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来源期刊

Journal of Structural Chemistry 化学-无机化学与核化学

CiteScore

1.60

自引率

12.50%

发文量

142

审稿时长

8.3 months

期刊介绍： Journal is an interdisciplinary publication covering all aspects of structural chemistry, including the theory of molecular structure and chemical bond; the use of physical methods to study the electronic and spatial structure of chemical species; structural features of liquids, solutions, surfaces, supramolecular systems, nano- and solid materials; and the crystal structure of solids.