期刊
CHEMICAL SCIENCE
卷 10, 期 2, 页码 587-593出版社
ROYAL SOC CHEMISTRY
DOI: 10.1039/c8sc04204g
关键词
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资金
- CREST, JST [JPMJCR13L3]
- JSPS KAKENHI [16K13609]
- Tokuyama Science Foundation
- Grants-in-Aid for Scientific Research [16K13609] Funding Source: KAKEN
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 M-6[Rh4Zn4O (l-cysteinate)(12)]nH(2)O (M-6[1]nH(2)O). In M-6[1]nH(2)O, 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 M-6[1]nH(2)O in the solid state increase in the order of Li-6[1]nH(2)O < Na-6[1]nH(2)O < K-6[1]nH(2)O, which is opposite to the order of the naked ionic radii. The conductivities reach the superionic level of sigma = 1.3 x 10(-2) S cm(-1) at 300 K for a single crystal of K-6[1]nH(2)O. These results reflect the high mobility of hydrated alkali metal ions in the crystal lattice of M-6[1]nH(2)O, 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 K-6[1]nH(2)O with Li+ and Na+ ions with retention of single crystallinity.
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