Composite Polymer Electrolyte Containing Ionic Liquid and Functionalized Polyhedral Oligomeric Silsesquioxanes for Anhydrous PEM Applications

Subianto, Surya; Mistry, Mayur K.; Choudhury, Namita Roy; Dutta, Naba K.; Knott, Robert

doi:10.1021/am900020w

Cited by 128 publications

(80 citation statements)

References 44 publications

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“…Subsequenta nion exhangew ith BF 4 À and PF 6 À provided allyl-min-BF 4 and allyl-min-PF 6 ,r espectively.I nc ontrast to previous reports, [9, 10,16] as imple thiol-ene reactionw as employedt op repare imidazolium-functionalized SQ-ILsb yu sing…”

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confidence: 51%

Rapid Preparation of Silsesquioxane‐Based Ionic Liquids

Liu

2016

Chemistry A European J

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Three new hybrid ionic liquids (ILs) based on cage silsesquioxane (SQ) were rapidly prepared in high yields from octa(mercaptopropyl)silsesquioxane and 1-allyl-3-methylimidazolium salts (Br(-), BF4(-), PF6(-)) through the photochemical thiol-ene reaction. These SQ-based ILs exhibited low glass transition temperatures and good thermal stability. The unique amphiphilic nature of these hybrid ILs cause them to self-assemble into perfect vesicles with "yolk-shell" structures, in which cages formed the "yolk" due to their aggregation and outer anions formed the "shell".

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confidence: 51%

Rapid Preparation of Silsesquioxane‐Based Ionic Liquids

Liu

2016

Chemistry A European J

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“…A wide variety of polyhedral oligomeric silsesquioxane (POSS)-based functional materials have been developed using ionic species. [10][11][12][13][14][15][16][17][18][19][20][21][22][23][24] We recently reported the synthesis of POSS-based ILs, and we investigated their thermal properties. 25,26 By tethering multiple ion pairs composed of imidazolium cations and carboxylates to the vertices of POSS cores or by simply adding POSS molecules with acid groups, the melting temperatures of the ion pairs decreased and their thermal stabilities increased.…”

Section: Introductionmentioning

confidence: 99%

POSS ionic liquid crystals

et al. 2015

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Here we report the use of unique organic − inorganic hybrid materials composed of octa-substituted polyhedral oligomeric silsesquioxane (POSS) cores as ionic liquid (IL) crystals. These materials have a wide temperature range in which they exist in liquid crystal (LC) phase because of the stabilizing effect of the POSS core. We synthesized ion pairs composed of alkyl chainsubstituted imidazolium and carboxylates of various lengths that were or were not connected to the POSS core; then the thermal properties of these materials were investigated. It was found that both ion salts and the octadecyl-substituted imidazolium ion pairs with or without connection to POSS could form LCs. Interestingly, the LC phase of the POSS-tethered ion salts was maintained until decomposition. In contrast, the octadecyl-substituted imidazolium ion salts that were not tethered to the POSS core showed a clearance point during heating. The highly symmetric structure of POSS contributes not only to the suppression of the molecular motion of the ion salts, but also results in the formation of regular structures, leading to thermally stable, thermotropic IL crystals. In addition, by using electrostatic interactions originating among ionic moieties, robust chiral structures can be produced. 3,4 Even a small quantity of chiral ionic sources can efficiently induce enantiomeric structures in a bulk sample, and ionic moieties can be assembled to form regularly ordered structures. 5,6 These well-ordered ionic moieties are expected to work as efficient cation carriers and scaffolds for ordering cations. These materials, which comprise closely assembled ionic species, can exhibit interesting optical and magnetic properties. Thus, new molecular designs for preparing thermally stable LCs composed of ionic species are needed to produce advanced functional materials.The concept of supported IL phases (SILPs) has been recently proposed. Several materials based on SILPs have exhibited important characteristics such as high ion conductivity and compatibility with organic reaction media; these materials have been used as templates for the formation of nanostructures. 1 Silica supports improve the thermal stability of LCs. 7,8 Carmichael et al. 9 have synthesized and explored silicon wafer-assisted SILP materials. They created layers with thicknesses between 10 and 21 nm of an ionic LC with [C 18 C 1 Im] [PF 6 ] on the planar wafer surface and found that the ionic LC formed a mesophase. Inspired by their work, Wasserscheid et al. 7 fabricated SILP materials using silicon nanoparticles and used them as supports for preparing mesoporous structures that could act as effective gasphase catalysts. 8 To construct advanced materials based on the concept of SILP materials, their properties must be fine-tuned according to preprogramed designs at the molecular level. A wide variety of

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“…[1][2][3][4][5][6][7][8][9][10][11][12][13][14][15] The increase in molecular weight and the presence of charges often cause an increase in the melting temperature. We have recently reported a polyhedral oligomeric silsesquioxane (POSS)-based room temperature IL that displays a melting temperature below 25 1C.…”

Section: Introductionmentioning

confidence: 99%

Thermodynamic study of POSS-based ionic liquids with various numbers of ion pairs

Tanaka

Ishiguro

Chujo

2011

Polym J

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We have previously reported a polyhedral oligomeric silsesquioxane (POSS)-based room temperature ionic liquid (IL) that shows a melting temperature below 25 1C. The connection of ion pairs to POSS can significantly improve the thermal stability and decrease the melting temperatures of the ion pairs. To understand the mechanism of these changes induced by POSS, we studied the thermal properties of POSS derivatives with variable numbers of imidazolium-carboxylate ion pairs. Initially, it was found that a modified POSS with a larger number of ion pairs could be a thermally stable, room temperature IL. From the series of thermodynamic and conformational analyses, we concluded that the star-shaped distribution of ion pairs originating from the cubic framework are necessary to express the characteristic changes in the thermal properties of ion pairs connected to POSS.

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Composite Polymer Electrolyte Containing Ionic Liquid and Functionalized Polyhedral Oligomeric Silsesquioxanes for Anhydrous PEM Applications

Cited by 128 publications

References 44 publications

Rapid Preparation of Silsesquioxane‐Based Ionic Liquids

Rapid Preparation of Silsesquioxane‐Based Ionic Liquids

POSS ionic liquid crystals

Thermodynamic study of POSS-based ionic liquids with various numbers of ion pairs

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