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Abstract <p>Nitrate REE complexes with a nitrosonium cation <b>(NO)</b><sub><b>3</b></sub><b>[</b><Emphasis Type="BoldItalic">Ln</Emphasis><sub><b>2</b></sub><b>(NO</b><sub><b>3</b></sub><b>)</b><sub><b>9</b></sub><b>]</b> <i>Ln</i>&#xa0;=&#xa0;La&#xa0;(<b>1</b>), Ce (<b>2</b>), Eu (<b>3</b>), Gd (<b>4</b>), Tb (<b>5</b>), Dy (<b>6</b>)); <b>(NO)</b><sub><b>2</b></sub><b>[</b><Emphasis Type="BoldItalic">Ln</Emphasis><b>(NO</b><sub><b>3</b></sub><b>)</b><sub><b>5</b></sub><b>]</b>, <i>Ln</i>&#xa0;=&#xa0;Er (<b>8</b>), Tm (<b>9</b>), Yb (<b>10</b>), Y (<b>11</b>); Na(NO)[Y(NO<sub>3</sub>)<sub>5</sub>] (<b>12</b>), Na(NO)[Y(NO<sub>3</sub>)<sub>5</sub>] (<b>13</b>), and NO[Ho(NO<sub>3</sub>)<sub>4</sub>] (<b>14</b>) 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 [<i>Ln</i>O<sub>12</sub>] (<i>Ln</i>&#xa0;=&#xa0;La–Dy) icosahedral polyhedron; island structures with a [<i>Ln</i>O<sub>10</sub>] (<i>Ln</i>&#xa0;=&#xa0;Er–Y) tetradodecahedron, and 1D chains in the case of holmium with an environment responding to a bicapped tetragonal antiprism. In <b>1</b>-<b>14,</b> NO<sup>+</sup> 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<sup>+</sup> coordination are considered. It is shown on the example of <b>3</b>, <b>6</b>, <b>10 </b>that thermolysis leads to consecutive formation of anhydrous nitrates, <i>Ln</i>ONO<sub>3</sub> oxonitrates, and REE oxides. The magnetic susceptibility study of <b>8</b> revealed no noticeable deviations from paramagnetic behavior.</p>

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

  • 期刊论文

  • 发表日期：

    2025年8月29日

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  • 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

摘要

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.