Conductive hybrid crystal composed of polyoxovanadate and deprotonatable ionic-liquid surfactant

Misawa, Toshiyuki; Koguchi, Shinichi; Niwa, Kanae; Kinoshita, Yuka; Uchida, Sayaka; Ito, Takeru

doi:10.1016/j.inoche.2018.07.040

Cited by 9 publications

(5 citation statements)

References 69 publications

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“…The DMT hybrid crystal contained diprotonated H 2 V 10 species exhibiting water sorption properties. The structural anisotropy in these V 10 -bolaamphiphile hybrid crystals will be intrinsically beneficial to the emergence of anhydrous proton conductivity at the intermediate temperature range, − which is under investigation. The methodology hybridizing polyoxometalate with bolaamphiphiles presented here would be promising to prepare another series of functional materials with respect to crystal engineering.…”

Section: Discussionmentioning

confidence: 99%

Porous Layered Inorganic–Organic Hybrid Frameworks Constructed from Polyoxovanadate and Bolaamphiphiles

Kiyota

Kojima

Kawahara

et al. 2021

Crystal Growth & Design

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Porous inorganic–organic hybrid crystals were successfully constructed from polyoxometalate anions and cationic bolaamphiphiles, which are surfactants having two hydrophilic heads in one molecule. The proton-affinitive decavanadate ([V10O28]6–, V10) anion was utilized as an inorganic motif. 1,10-Decamethylenediammonium ([H3N(CH2)10NH3]2+, DDA) and decamethonium ([(H3C)3N(CH2)10N(CH3)3]2+, DMT) bolaamphiphiles were employed as organic cations. Three types of DDA-V10 hybrid crystals were obtained under different crystallization conditions, and the number of proton(s) attached to each V10 anion was controllable from 0 to 2. This induced different ratios of the V10 species and DDA cations in the hybrid crystals, which enabled control of the crystal packings. The DMT cation gave a hybrid crystal comprising a diprotonated V10 species. These hybrid crystals possessed distinct layered structures derived from the presence of bolaamphiphiles, which resulted in anisotropic alignments of constituent molecules including solvents of crystallization. The solvent molecules were one-dimensionally aligned in the crystals and could be removed to form gas-accessible voids. Specifically, DDA-V10 hybrid crystals sorbed CO2 and C2H2 molecules into the hydrophobic voids, while the DMT-V10 hybrid crystal had affinity against the H2O sorbent.

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Section: Discussionmentioning

confidence: 99%

Porous Layered Inorganic–Organic Hybrid Frameworks Constructed from Polyoxovanadate and Bolaamphiphiles

Kiyota

Kojima

Kawahara

et al. 2021

Crystal Growth & Design

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“…[121][122][123] On the other hand the CTA surfactant has led to single-crystalline structures [124,125] that provide insight into the arrangement of POMs and QA(AP)s in numerous hybrid phases discussed in this section. The SECs with their bulky shell of long-chain hydrocarbons can be dissolved in organic solvents and these can be transferred to a surface for molecular devices with electrochemical or electrochromic response, catalytic function, [123,126] gas adsorption, [123] or Li + [127] or H + [128] conduction for energy conversion and storage. Organically-soluble SECs have also been proposed for applications including stabilization of emulsions, [129] extraction and separation of uranium [130] and NMR paramagnetic relaxation reagents.…”

Section: Angewandte Chemiementioning

confidence: 99%

Beyond Charge Balance: Counter‐Cations in Polyoxometalate Chemistry

et al. 2019

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Polyoxometalates (POMs) are molecular metal‐oxide anions applied in energy conversion and storage, manipulation of biomolecules, catalysis, as well as materials design and assembly. Although often overlooked, the interplay of intrinsically anionic POMs with organic and inorganic cations is crucial to control POM self‐assembly, stabilization, solubility, and function. Beyond simple alkali metals and ammonium, chemically diverse cations including dendrimers, polyvalent metals, metal complexes, amphiphiles, and alkaloids allow tailoring properties for known applications, and those yet to be discovered. This review provides an overview of fundamental POM–cation interactions in solution, the resulting solid‐state compounds, and behavior and properties that emerge from these POM–cation interactions. We will explore how application‐inspired research has exploited cation‐controlled design to discover new POM materials, which in turn has led to the quest for fundamental understanding of POM–cation interactions.

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“…The electrostatic interaction of POMs with different types of cationic organic units in solutions under controlled conditions (concentrations of the reagents, pH, temperature, and reaction time) was shown to result in nanostructures of various forms and sizes and with different properties 20b,23,77–83. For instance, combining the [V 10 O 28 ] 6– polyanions with 1-dodecylimidazolium (C 12 im) cations yielded a hybrid [C 3 H 4 N 2 (C 12 H 25 )] 4 [H 2 V 10 O 28 ]·0.5C 2 H 5 OH compound that was found to exhibit anhydrous proton conductivity (4.6 × 10 –5 S cm –1 at 373 K) 78. The electrostatic interaction of long-chain quaternary ammonium cations with POMs led to supramolecular materials23,79,80 whose application areas range from protective coating for natural stones23 to water treatment 80.…”

Section: Pom-based Supramolecular Hybrid Compoundsmentioning

confidence: 99%