Synthesis and functionalities of FeSn12 superatom prepared by single atom introduction with a dendrimer template.

Superatoms are promising as new building block materials that can be designed by precise controlling of the constituent atoms. Stannaspherene (Sn12 2-) is a rigid cage-like cluster with icosahedral symmetry, for which one-atom encapsulation was theoretically expected and detected in the gas phase. Here, a single-atom introduction method into stannaspherene using a dendrimer template with polyvinylpyrrolidone (PVP) protection is demonstrated. This advanced solution-phase synthesis allows not only the selective doping of one atom into the cluster cage, but also enable further detail characterization of optical and magnetic properties that were not possible in the gas-phase synthesis. In other words, this liquid-phase synthesis method has enabled the adaptation of detailed analytical methods. In this study, FeSn12 was synthesized and characterized, revealing that a single Fe atom introduction in the Sn12 2- cage result in the appearance of near-infrared emission and enhancement in the magnetism.

Liquid crystalline 2D borophene oxide for inorganic optical devices.

Borophene has been recently proposed as a next-generation two-dimensional material with promising electronic and optical properties. However, its instability has thus far limited its large-scale applications. Here, we investigate a liquid-state borophene analogue with an ordered layer structure derived from two-dimensional borophene oxide. The material structure, phase transition features and basic properties are revealed by using X-ray analysis, optical and electron microscopy, and thermal characterization. The obtained liquid crystal exhibits high thermal stability at temperatures up to 350 °C and an optical switching behaviour driven by a low voltage of 1 V.

Solution Phase Mass Synthesis of 2D Atomic Layer with Hexagonal Boron Network.

Borophene and the analogs are attractive 2D-materials showing unique mechanical and electronic properties. In this study, the bottom-up synthesis of an atomic boron network possessing a completely planar skeleton was achieved from KBH4. The borophene-analog was stabilized by oxygen atoms positioned on the same plane, providing holes and the anionic state of the layer. Potassium cations between the layers enabled crystalline stacking of the layers, as well as dissolution in solvents as atomically thin layers. The conductivity measurements revealed the electronic feature. Unlike the interplane conducting property, almost zero activation energy like a metal was suggested from the in-plane measurement.

Effect of the ammonium ion on proton conduction in porous ionic crystals based on Keggin-type silicododecatungstate.

Proton conduction in crystalline porous materials has received much attention from basic scientific research through to practical applications. Polyoxometalates (POMs) can efficiently transport protons because of their small superficial negative charge density. A simple method for enhancing proton conductivity is to introduce NH4+ into the crystal structure, because NH4+ can form hydrogen bonds and function as a proton carrier. According to these considerations, NH4+ was introduced into the porous structure of A2[Cr3O(OOCH)6(etpy)3]2[α-SiW12O40]·nH2O (A = Li, Na, K and Cs; etpy = 4-ethylpyridine) (I-A+) via topotactic cation exchange. The resulting compound, diammonium tris(4-ethylpyridine)hexaformatooxidotrichromium α-silicododecatungstate hexahydrate, (NH4)2[Cr3(CHO2)6O(C7H9N)3]2[α-SiW12O40]·6H2O, showed high proton conductivity and low activation energy under high relative humidity (RH), suggesting that protons migrate efficiently via rearrangement of the hydrogen-bonding network formed by the NH4+ cations and the waters of crystallization (Grotthuss mechanism). The proton conductivity and activation energy greatly decreased and increased, respectively, with the decrease in RH, suggesting that protons migrate as NH4+ and/or H3O+ under low RH (vehicle mechanism).

Proton conduction in alkali metal ion-exchanged porous ionic crystals.

Proton conduction in alkali metal ion-exchanged porous ionic crystals A2[Cr3O(OOCH)6(etpy)3]2[α-SiW12O40]·nH2O [I-A+] (A = Li, Na, K, Cs, etpy = 4-ethylpyridine) is investigated. Single crystal and powder X-ray diffraction measurements show that I-A+ possesses analogous one-dimensional channels where alkali metal ions (A+) and water of crystallization exist. Impedance spectroscopy and water diffusion measurements of I-A+ show that proton conductivities are low (10-7-10-6 S cm-1) under low relative humidity (RH), and protons mostly migrate as H3O+ with H2O as vehicles (vehicle mechanism). The proton conductivity of I-A+ increases with the increase in RH and is largely dependent on the types of alkali metal ions. I-Li+ shows a high proton conductivity of 1.9 × 10-3 S cm-1 (323 K) and a low activation energy of 0.23 eV under RH 95%. Under high RH, alkali metal ions with high ionic potentials (e.g., Li+) form a dense and extensive hydrogen-bonding network of water molecules with mobile protons at the periphery, which leads to high proton conductivities and low activation energies via rearrangement of the hydrogen-bonding network (Grotthuss mechanism).