Affinities of crown ethers, glymes, and polyamines for alkali picrates in toluene. Application of polymer-supported linear polyethers

Xu, Wen Ying; Smid, Johannes

doi:10.1021/ja00325a013

Cited by 36 publications

(18 citation statements)

References 5 publications

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“…These results suggest that DMC did not coordinate with LiTf salt in an ocean of PEO chains. This is consistent with literature reports. ,,,, Generally, a carbonate group forms looser bonding to Li + compared to an EO group. − …”

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confidence: 92%

Determining and Minimizing Resistance for Ion Transport at the Polymer/Ceramic Electrolyte Interface

et al. 2019

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In this work, we report methods to quantify and minimize the interfacial resistance for Li ion transport, R interface , between a model polymer electrolyte, poly-(ethylene oxide) + LiCF 3 SO 3 (PE), and a model Li +conducting ceramic electrolyte, LICGC from Ohara Corporation. By constructing a PE−ceramic−PE trilayer cell, we found R interface to be very large, 1.2 kΩ•cm 2 at 30 °C, accounting for 66% of the total trilayer cell resistance. When dimethyl carbonate, a loose-binding solvent of Li + , was introduced into the trilayer, R interface decreased to essentially zero. As a result, a composite electrolyte with carbonate plasticizers wherein 40 vol % ceramic particles were dispersed in the polymer showed extraordinary room-temperature conductivity of approximately 10 −4 S/cm, 3 orders of magnitude higher than that of the dry composite electrolyte. This discovery can be used as guidance in designing composite electrolytes to achieve synergistic effects.

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supporting

confidence: 92%

Determining and Minimizing Resistance for Ion Transport at the Polymer/Ceramic Electrolyte Interface

et al. 2019

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“…While the literature does not contain values for cation binding by a nonfluorinated analogue of tetraether 4 under matching conditions, the binding constant of 2.74 × 10 4 M -1 for Li + binding to triethylene glycol dimethyl ether in 199:1 toluenetetrahydrofuran illustrates the much stronger affinity of nonfluorinated polyethers for alkali metal ions. 45 In the absence of further experimental data, it is unclear whether the one single hydrogen atom of tetraether 4 has any appreciable effect on the stability of its cation complexes. We will further investigate how different numbers of fluorine atoms affect the shape and population of molecular orbitals and cation binding of perfluorinated ethers using experimental and computational means.…”

Section: Resultsmentioning

confidence: 99%

Coordinative Properties of Highly Fluorinated Solvents with Amino and Ether Groups

et al. 2005

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In spite of the widespread use of perfluorinated solvents with amino and ether groups in a variety of application fields, the coordinative properties of these compounds are poorly known. It is generally assumed that the electron withdrawing perfluorinated moieties render these functional groups rather inert, but little is known quantitatively about the extent of their inertness. This paper reports on the interactions between inorganic monocations and perfluorotripentylamine and 2H-perfluoro-5,8,11-trimethyl-3,6,9,12-tetraoxapentadecane, as determined with fluorous liquid-membrane cationselective electrodes doped with tetrakis[3,5-bis(perfluorohexyl)phenyl]borate salts. The amine does not undergo measurable association with any ion tested, and its formal pK a is shown to be smaller than -0.5. This is consistent with the nearly planar structure of the amine at its nitrogen center, as obtained with density functional theory calculations. The tetraether interacts very weakly with Na + and Li + . Assuming 1:1 stoichiometry, formal association constants were determined to be 2.3 and 1.5 M -1 , respectively. This disproves an earlier proposition that the Lewis base character in such compounds may be non-existent. Due to the extremely low polarity of fluorous solvents and the resulting high extent of ion pair formation, a fluorophilic electrolyte salt with perfluoroalkyl substituents on both the cation and the anion had to be developed for these experiments. In its pure form, this first fluorophilic electrolyte salt is an ionic liquid with a glass transition temperature, T g , of -18.5 °C. Interestingly, the molar conductivity of solutions of this salt increases very steeply in the high concentration range, making it a particularly effective electrolyte salt.

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“…Vm and wim determined for the present system were 0.48 mL and 1.01 x 10~4 mol, respectively. We can thus use 4.75 for the following calculation in place of l/[M+(s)]<£ and finally obtain l/k'• 4.75(1 + 2-^)/ Wi...4iCMH (6) ;…”

Section: Resultsmentioning

confidence: 99%

Efficient evaluation of poly(oxyethylene) complex formation with alkali-metal cations

Okada¹

1990

Macromolecules

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An efficient method is developed for the evaluation of the complexation of poly-(oxyethylenes) (POE) with alkali-metal cations in solution. Equations derived from equilibria controlling the chromatographic retention allow us to determine the complex formation constants of a variety of POE oligomers contained in polydisperse POE samples. Statistical consideration shows that compounds having less than 16 repeating oxyethylene (EO) units form only 1:1 complexes whereas those having more than 17 EO units form 1:1 and 2:1 complexes (cation-POE) with K+ or Rb+ and that the POEs tested do not form 3:1 or higher multiple complexes.

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Affinities of crown ethers, glymes, and polyamines for alkali picrates in toluene. Application of polymer-supported linear polyethers

Cited by 36 publications

References 5 publications

Determining and Minimizing Resistance for Ion Transport at the Polymer/Ceramic Electrolyte Interface

Determining and Minimizing Resistance for Ion Transport at the Polymer/Ceramic Electrolyte Interface

Coordinative Properties of Highly Fluorinated Solvents with Amino and Ether Groups

Efficient evaluation of poly(oxyethylene) complex formation with alkali-metal cations

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