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Mobility of hydrated alkali metal ions in metallosupramolecular ionic crystals

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Abstract

The design and creation of ionic crystals that show high mobility of ionic species in the solid state has long been a research topic of considerable attention not only due to the practical applications of these materials but also due to the correlation of such ionic species with ion-transport biological systems. In this work, we report the mobility of alkali metal ions (M = Li+, Na+, K+) in the ionic crystals M6[Rh4Zn4O (L-cysteinate)12nH2O (M6[1nH2O). In M6[1nH2O, alkali metal ions are distributed in a disordered manner, together with a number of water molecules, within a rigid hydrogen-bonded framework of anionic clusters of [1]6−. The alternating current conductivities of M6[1nH2O in the solid state increase in the order of Li6[1nH2O < Na6[1nH2O < K6[1nH2O, which is opposite to the order of the naked ionic radii. The conductivities reach the superionic level of σ = 1.3 × 10−2 S cm−1 at 300 K for a single crystal of K6[1nH2O. These results reflect the high mobility of hydrated alkali metal ions in the crystal lattice of M6[1nH2O, which is supported by solid-state NMR spectroscopy, together with ion diffusion experiments in the solid state. The high mobility leads to quick exchange of K+ ions in K6[1nH2O with Li+ and Na+ ions with retention of single crystallinity.

Graphical abstract: Mobility of hydrated alkali metal ions in metallosupramolecular ionic crystals

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Publication details

The article was received on 21 Sep 2018, accepted on 20 Oct 2018 and first published on 26 Oct 2018


Article type: Edge Article
DOI: 10.1039/C8SC04204G
Citation: Chem. Sci., 2019, Advance Article
  • Open access: Creative Commons BY-NC license
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    Mobility of hydrated alkali metal ions in metallosupramolecular ionic crystals

    N. Yoshinari, S. Yamashita, Y. Fukuda, Y. Nakazawa and T. Konno, Chem. Sci., 2019, Advance Article , DOI: 10.1039/C8SC04204G

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