Controlled introduction of metal cations into polymerizable ionic liquid-polyoxomolybdate hybrid crystals

Kobayashi, Jun; Misawa, Toshiyuki; Umeda, Chihiro; Isono, Toru; Ono, Seiji; Naruke, Haruo; Okamura, Yosuke; Koguchi, Shinichi; Higuchi, Masashi; Yu, Na; Ito, Takeru

doi:10.1039/c8ce01658e

Cited by 10 publications

(12 citation statements)

References 64 publications

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“…X-ray structure analyses together with CHN elemental analyses revealed that the Mo 8 hybrid crystals were formulated to be [{CH 2 =C(CH 3 )COO(CH 2 ) 2 }C 3 H 4 N 2 ] 3 Na[Mo 8 O 26 ] for 1 and [{CH 2 =C(CH 3 )COO(CH 2 ) 2 }C 3 H 3 N 2 (C 8 H 17 )] 3 Na[Mo 8 O 26 ] for 2 , respectively (Table 1, Figure 3). Both hybrid crystals contained three MAIm (1+ charge) or MAImC 8 (1+ charge) and one Na + associated with one β-type Mo 8 anion (4− charge), being similar to other hybrid crystals consisting of β-type Mo 8 anions [42,53,54]. Both crystal structures contained a one-dimensional (1D) infinite chain composed of the Na + cation and Mo 8 anion (Mo 8 –Na + 1D chain) as shown in Figure 3a,b, while the coordination environments of Na + were different.…”

Section: Resultsmentioning

confidence: 52%

“…The POM anions hybridized were β-type octamolybdate ([Mo 8 O 26 ] 4– (Mo 8 ), Figure 1b) and dodecatungstosilicate ([SiW 12 O 40 ] 4– (SiW 12 ), Figure 1b), both of which are anions with a 4− charge. Hybrid crystals with Mo 8 and SiW 12 have been reported previously [42,44]. The hybrid crystals with MAImC 8 contained anisotropic arrangements of POM anions in their bulk crystal structures due to the presence of an amphiphilic moiety, while hybrid crystals with MAIm exhibited isotropic POM arrangements.…”

Section: Introductionmentioning

confidence: 69%

“…All chemical reagents were purchased from FUJIFILM Wako Pure Chemical Corporation (Osaka, Japan) and Tokyo Chemical Industry Co., Ltd. (TCI, Tokyo, Japan). The starting polymerizable ionic liquid of [{CH 2 =C(CH 3 )COO(CH 2 ) 2 }C 3 H 3 N 2 ] (denoted as MAIm–N) was synthesized as a neutral compound, and [{CH 2 =C(CH 3 )COO(CH 2 ) 2 }C 3 H 3 N 2 (C 8 H 17 )]Br (MAImC 8 ·Br) were synthesized as bromide salts according to previous studies (Figure S1) [42,43,44].…”

Section: Methodsmentioning

confidence: 99%

“…Recently, we designed a polymerizable ionic liquid cation with an imidazolium moiety with a methacryloyl group ([{CH 2 =C(CH 3 )COO(CH 2 ) 2 }C 3 H 3 N 2 (CH 3 )] + , denoted as MAImC 1 , Figure 1a), and successfully synthesized inorganic–organic hybrid monomers and polymers with several POM anions [42,43,44]. These MAImC 1 –POM hybrids were isolated as single crystals with clarified structures, and behaved as monomers of hybrid polymers exhibiting high conductivity as solid electrolytes [44].…”

Section: Introductionmentioning

confidence: 99%

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Dimensional Control in Polyoxometalate Crystals Hybridized with Amphiphilic Polymerizable Ionic Liquids

et al. 2019

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Ionic liquids are an important component for constructing functional materials, and polyxometalate cluster anion is a promising partner for building inorganic–organic hybrid materials comprising ionic liquids. In such hybrid materials, the precise control of the molecular arrangement in the bulk structures is crucial for the emergence of characteristic functions, which can be realized by introducing an amphiphilic moiety into the ionic liquids. Here, an amphiphilic polymerizable imidazolium ionic liquid with a methacryloyl group was firstly hybridized with polyoxometalate anions of octamolybdate ([Mo8O26]4−, Mo8) and silicotungstate ([SiW12O40]4−, SiW12) to obtain inorganic–organic hybrid crystals. The polymerizable ionic liquid with a octyl chain (denoted as MAImC8) resulted in the formation of anisotropic molecular arrangements in the bulk crystal structure, which was compared with the hybrid crystals composed from the polymerizable ionic liquid without a long alkyl chain (denoted as MAIm). Rather densely packed isotropic molecular arrangements were observed in the hybrid crystals of MAIm–Mo8 and MAIm–SiW12 due to the lack of the amphiphilic moiety. On the other hand, using the amphiphilic MAImC8 cation gave rise to a honeycomb-like structure with the Mo8 anion and a layered structure with the SiW12 anion, respectively.

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Section: Resultsmentioning

confidence: 52%

Section: Introductionmentioning

confidence: 69%

Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Dimensional Control in Polyoxometalate Crystals Hybridized with Amphiphilic Polymerizable Ionic Liquids

et al. 2019

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“…Several POMs with covalently-grafted polymerizable group have been prepared in a molecularly precise way to form hybrid polymers [38][39][40][41][42][43][44][45][46][47][48][49][50], while the POMs which can be organically modified are very limited to the specific POM species. More versatile but rarely reported method is to utilize polymerizable cations to prepare the hybrid "monomer" with POM anions, which can be polymerized into inorganic-organic hybrid polymers [24,[51][52][53][54].…”

Section: Introductionmentioning

confidence: 99%

Highly Conductive Polymer Electrolytes Constructed from Polymerizable Ionic-Liquid and Inorganic Cluster

Ito

Kiyota

Oda

et al. 2019

Trans. Mat. Res. Soc. Japan

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Conductive inorganic-organic hybrid monomers and polymers were successfully obtained by using a polymerizable imidazolium ionic-liquid with a methacryloyl group (denoted as MAImC 1) and inorganic polyoxometalate cluster anion ([SiW 12 O 40 ] 4− , SiW 12). The MAImC 1-SiW 12 hybrid monomer was synthesized as single crystals, the molecular and crystal structures of which were revealed by single crystal X-ray analysis. The obtained MAImC 1-SiW 12 hybrid monomer was found to be polymerized by a radical polymerization using AIBN as an initiator to form inorganic-organic homo-and copolymers. The hybrid copolymers of MAImC 1-SiW 12 polymerized with another polymerizable ionic-liquid (denoted as MAImC 8) exhibited high conductivity of 10 −3 S cm −1 order under humidified condition at near room temperature of 313 K.

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Inorganic‐Organic Hybrid Crystals Derived from Polyoxovanadate and Ionic‐Liquid toward Promising Conductive Materials

Kiyota,

Ono,

Sasaki

et al. 2024

ChemNanoMat

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Conductive polyoxovanadate inorganic‐organic hybrid crystals comprising alkaline earth metal (divalent) cations were successfully obtained with the use of an ionic‐liquid cation having imidazolium and methacryloyl moieties (denoted as MAImC1). Two types of crystals containing decavanadate ([V10O28]6‒, V10) anion were obtained as [MAImC1]2Ca2[V10O28]·16H2O·2C2H5OH (MAImC1‐Ca‐V10) and [MAImC1]2Mg2[V10O28]·18H2O·2C2H5OH (MAImC1‐Mg‐V10). Connection modes of the divalent cations were different: Ca2+ cations were connected to V10 to form a {[Ca(H2O)5]2V10O28]}2‒ anion in MAImC1‐Ca‐V10, while a discrete [V10O28]6‒ and hydrated [Mg(H2O)6]2+ were present in MAImC1‐Mg‐V10. Conductivities under a fully humidified condition at 353 K (80 °C) were high values of 3.0 × 10–4 S cm–1 for MAImC1‐Ca‐V10 and 3.3 × 10–3 S cm–1 for MAImC1‐Mg‐V10, respectively. The higher conductivity under hydrated conditions suggests proton as a conductive carrier. The better conductivity of MAImC1‐Mg‐V10 is plausibly derived from the more effective hydrogen‐bonded network in the crystal lattice.

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Controlled introduction of metal cations into polymerizable ionic liquid-polyoxomolybdate hybrid crystals

Abstract: The first syntheses of polyoxomolybdate hybrid crystals were achieved by using polymerizable ionic-liquid.

Cited by 10 publications

References 64 publications

Dimensional Control in Polyoxometalate Crystals Hybridized with Amphiphilic Polymerizable Ionic Liquids

Dimensional Control in Polyoxometalate Crystals Hybridized with Amphiphilic Polymerizable Ionic Liquids

Highly Conductive Polymer Electrolytes Constructed from Polymerizable Ionic-Liquid and Inorganic Cluster

Inorganic‐Organic Hybrid Crystals Derived from Polyoxovanadate and Ionic‐Liquid toward Promising Conductive Materials

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