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Mobility of hydrated alkali metal ions in metallosupramolecular ionic crystals.

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)12]·nH2O (M6[1]·nH2O). In M6[1]·nH2O, 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[1]·nH2O in the solid state increase in the order of Li6[1]·nH2O < Na6[1]·nH2O < K6[1]·nH2O, which is opposite to the order of the naked ionic radii. The conductivities reach the superionic level of ? = 1.3 × 10-2 S cm-1 at 300 K for a single crystal of K6[1]·nH2O. These results reflect the high mobility of hydrated alkali metal ions in the crystal lattice of M6[1]·nH2O, 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[1]·nH2O with Li+ and Na+ ions with retention of single crystallinity.

SUBMITTER: Yoshinari N

PROVIDER: S-EPMC6335618 | biostudies-literature | 2019 Jan

REPOSITORIES: biostudies-literature

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Mobility of hydrated alkali metal ions in metallosupramolecular ionic crystals.

Yoshinari Nobuto N Yamashita Satoshi S Fukuda Yosuke Y Nakazawa Yasuhiro Y Konno Takumi T

Chemical science 20181026 2

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-cystein ...[more]

PMID: 30746100

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Project description:The hydration of the alkali metal ions in aqueous solution has been studied by large angle X-ray scattering (LAXS) and double difference infrared spectroscopy (DDIR). The structures of the dimethyl sulfoxide solvated alkali metal ions in solution have been determined to support the studies in aqueous solution. The results of the LAXS and DDIR measurements show that the sodium, potassium, rubidium and cesium ions all are weakly hydrated with only a single shell of water molecules. The smaller lithium ion is more strongly hydrated, most probably with a second hydration shell present. The influence of the rubidium and cesium ions on the water structure was found to be very weak, and it was not possible to quantify this effect in a reliable way due to insufficient separation of the O-D stretching bands of partially deuterated water bound to these metal ions and the O-D stretching bands of the bulk water. Aqueous solutions of sodium, potassium and cesium iodide and cesium and lithium hydroxide have been studied by LAXS and M-O bond distances have been determined fairly accurately except for lithium. However, the number of water molecules binding to the alkali metal ions is very difficult to determine from the LAXS measurements as the number of distances and the temperature factor are strongly correlated. A thorough analysis of M-O bond distances in solid alkali metal compounds with ligands binding through oxygen has been made from available structure databases. There is relatively strong correlation between M-O bond distances and coordination numbers also for the alkali metal ions even though the M-O interactions are weak and the number of complexes of potassium, rubidium and cesium with well-defined coordination geometry is very small. The mean M-O bond distance in the hydrated sodium, potassium, rubidium and cesium ions in aqueous solution have been determined to be 2.43(2), 2.81(1), 2.98(1) and 3.07(1) Å, which corresponds to six-, seven-, eight- and eight-coordination. These coordination numbers are supported by the linear relationship of the hydration enthalpies and the M-O bond distances. This correlation indicates that the hydrated lithium ion is four-coordinate in aqueous solution. New ionic radii are proposed for four- and six-coordinate lithium(I), 0.60 and 0.79 Å, respectively, as well as for five- and six-coordinate sodium(I), 1.02 and 1.07 Å, respectively. The ionic radii for six- and seven-coordinate K(+), 1.38 and 1.46 Å, respectively, and eight-coordinate Rb(+) and Cs(+), 1.64 and 1.73 Å, respectively, are confirmed from previous studies. The M-O bond distances in dimethyl sulfoxide solvated sodium, potassium, rubidium and cesium ions in solution are very similar to those observed in aqueous solution.

Dataset Information

Mobility of hydrated alkali metal ions in metallosupramolecular ionic crystals.

Publications

Mobility of hydrated alkali metal ions in metallosupramolecular ionic crystals.

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