Issue 10, 2020

Crystallization of colourless hexanitratoneptunate(iv) with anhydrous H+ countercations trapped in a hydrogen bonded polymer with diamide linkers

Abstract

Colourless crystalline compounds of centrosymmetric [Np(NO3)6]2− were yielded from 3 M HNO3 aq in the presence of double-headed 2-pyrrolidone derivatives (L). In the obtained crystal structures, H+ was also involved as a countercation to compensate for the negative charge of [Np(NO3)6]2−, where the initial hydration around H+ was fully removed during crystallization despite it having the strongest hydration enthalpy. Instead, this anhydrous H+ was captured by L to form a [H+L]n hydrogen bonded polymer. In [Np(NO3)6]2−, the Np4+ centre is twelve-coordinated with 6 bidentate NO3, and therefore, present in an icosahedral geometry bearing inversion centre. In such a centrosymmetric system, any f–f transitions stemming from the 5f3 electronic configuration of Np4+ are electric-dipole forbidden. This is the reason why the compounds currently obtained were colourless unlike ordinary Np(IV) species, which are olive-green.

Graphical abstract: Crystallization of colourless hexanitratoneptunate(iv) with anhydrous H+ countercations trapped in a hydrogen bonded polymer with diamide linkers

Supplementary files

Article information

Article type
Paper
Submitted
02 Dez 2019
Accepted
31 Jan 2020
First published
07 Feb 2020
This article is Open Access
Creative Commons BY license

RSC Adv., 2020,10, 6082-6087

Crystallization of colourless hexanitratoneptunate(IV) with anhydrous H+ countercations trapped in a hydrogen bonded polymer with diamide linkers

K. Takao, J. März, M. Matsuoka, T. Mashita, H. Kazama and S. Tsushima, RSC Adv., 2020, 10, 6082 DOI: 10.1039/C9RA10090C

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