Cation-Cation Interaction in Np(V) Perchlorates and Their Electronic Absorption Spectra
Mikhail S Grigoriev1, Alexei A Bessonov1, Iraida A Charushnikova1
1Frumkin Institute of Physical Chemistry and Electrochemistry, Russian Academy of Sciences, Bldg 4, 31 Leninsky Prosp., Moscow 119071, Russian Federation.
Abstract:
Four new Np(V) perchlorate complexes of the composition [NpO2(H2O)4]ClO4 (orthorhombic) (1), [(NpO2)2(ClO4)(H2O)4]ClO4·H2O (3), [(NpO2)(UO2)(H2O)8](ClO4)3 (4), and [(NpO2)2Cl(H2O)4]ClO4·2H2O (5) have been synthesized and structurally characterized. The structure of previously known monoclinic modification of NpO2ClO4·4H2O (2) has been determined at 100 K. The coordination environment of Np and U atoms in compounds 1-5 is pentagonal bipyramids. A cation-cation (CC) interaction was found in structures 1-5, in which the NpO2+ ion manifests itself as a monodentate (1, 2) or bidentate (3-5) ligand. CC bonds play a fundamental role in the crystal structures of compounds 1, 2, and 4. 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.
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