Cation–Cation Interaction in Np(V) Perchlorates and Their Electronic Absorption Spectra
Four new Np(V) perchlorate complexes of the composition [NpO<sub>2</sub>(H<sub>2</sub>O)<sub>4</sub>]ClO<sub>4</sub> (orthorhombic) (<b>1</b>), [(NpO<sub>2</sub>)<sub>2</sub>(ClO<sub>4</sub>)(H<sub>2</sub>O)<sub>4</sub>]ClO<sub>4</sub>·H<sub>2</sub>O (<b>3</b>), [(NpO<sub>2</sub>)(UO<sub>2</sub>)(H<sub>2</sub>O)<sub>8</sub>](ClO<sub>4</sub>)<sub>3</sub> (<b>4</b>), and [(NpO<sub>2</sub>)<sub>2</sub>Cl(H<sub>2</sub>O)<sub>4</sub>]ClO<sub>4</sub>·2H<sub>2</sub>O (<b>5</b>) have been synthesized and structurally characterized. The structure of previously known monoclinic modification of NpO<sub>2</sub>ClO<sub>4</sub>·4H<sub>2</sub>O (<b>2</b>) has been determined at 100 K. The coordination environment of Np and U atoms in compounds <b>1</b>-<b>5</b> is pentagonal bipyramids. A cation-cation (CC) interaction was found in structures <b>1</b>-<b>5</b>, in which the NpO<sub>2</sub><sup>+</sup> ion manifests itself as a monodentate (<b>1</b>, <b>2</b>) or bidentate (<b>3</b>-<b>5</b>) ligand. CC bonds play a fundamental role in the crystal structures of compounds <b>1</b>, <b>2</b>, and <b>4</b>. They are the main structure-forming bonds that form the crystal package as a whole. The spectra of all compounds in the visible-near-IR range were measured.
Authors
- A. A. Bessonov (ORCID: https://orcid.org/0000-0003-1758-7349)
- I. A. Charushnikova (ORCID: https://orcid.org/0000-0001-5442-5459)
- Mikhail S. Grigoriev (ORCID: https://orcid.org/0000-0002-6363-5535)
- Nikolay N. Krot
Institutions
- Frumkin Institute of Physical Chemistry and Electrochemistry Russian Academy of Sciences (RU)
Publication Details
- Journal
- Inorganic Chemistry
- Published
- 2024-12-18
- DOI
- https://doi.org/10.1021/acs.inorgchem.4c04440
- Citations
- 1
- Primary Topic
- Radioactive element chemistry and processing
- Type
- article
- Field-Weighted Citation Impact
- 0.16
Funders
- Ministry of Science and Higher Education of the Russian Federation