A study of the cesium cation bonding to carboxylate anions by the kinetic method and quantum chemical calculations

Mayeux, Charly; Gal, Jean‐François; Charles, Laurence; Massi, Lionel; Maria, Pierre‐Charles; Tammiku-Taul, Jaana; Lohu, Ene-Liis; Burk, Peeter

doi:10.1002/jms.1735

Cited by 11 publications

(14 citation statements)

References 38 publications

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“…Figure b shows a comparison of d layer of telechelic PEs and the estimated layer-to-layer distances ( d 0 ) with all-trans chain conformation and no chain tilt. The ionic bond lengths between the carboxylate groups and metal cations were calculated based on references values. ,− The fact that all d layer are slightly smaller than d 0 suggests that the chain conformations are extended across the crystalline domain and the alkyl segments are tilted relative to the ionic basal plane in the crystals (Figure a). The estimated chain tilt angle (Φ) was calculated using .…”

Section: Resultsmentioning

confidence: 99%

Monodisperse and Telechelic Polyethylenes Form Extended Chain Crystals with Ionic Layers

Häußler

Bauer

et al. 2019

Macromolecules

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We report the synthesis of ionic telechelic low-molecular-weight polyethylenes (PEs) with precise chain lengths that are derived from plant oils along with their morphologies and temperature-dependent ionic conductivities. Starting from the C48 telechelic dimethyl ester, or the C23 analogue for comparison, different ionic carboxylate end groups (H+, Na+, Cs+, Zn2+) were introduced by microwave-assisted saponification chemistry. Because of the precise length of the polymethylene sequence, these difunctional telechelic PEs crystallize into exceptionally well-ordered nanoscale-layered structures at room temperature. As a consequence of their extended chain crystal nature, the layer thickness is directly encoded by the telechelic molecules methylene chain length. Notably, C21(COONa)2, C46(COONa)2, and C46(COOCs)2 exhibit transitions in the crystalline structure prior to the fully disordered melt state, as evidenced by differential scanning calorimetry and in situ X-ray scattering. The melting transition is typically accompanied by a transition from layered ionic nanoaggregates between the crystallites to disordered ionic aggregates, with an interesting exception wherein the ionic layers transform to hexagonal symmetry. The temperature-dependent ionic conductivities of layered crystalline morphologies in the C48 materials exhibit an Arrhenius-like behavior, indicating a decoupling from the slower polymer segmental motions at T < T m. These new precise ionic telechelic PEs produce well-defined nanoscale-layered morphologies with tunable ion transport properties that could be further developed as solid-state electrolytes.

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Section: Resultsmentioning

confidence: 99%

Monodisperse and Telechelic Polyethylenes Form Extended Chain Crystals with Ionic Layers

Häußler

Bauer

et al. 2019

Macromolecules

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“…These assumptions have been checked in our work on Cs + and were found to hold. 8 In a previous computational study, it was noticed that the calculated entropies of heterolytic dissociation of cesium benzoates exhibited close values, with the possible exception of the orthosubstituted compounds, 59 because of metal chelation. Entropy changes for the five series fall in a narrow range of less than ±10 J mol −1 K −1 (Table S3) corresponding to an added uncertainty of less than ±3 kJ mol −1 on enthalpies.…”

Section: ■ Experimental Sectionmentioning

confidence: 93%

“…The ln(I/I 0 ) scales obtained from multiple regression analysis for all cations are summarized in Table 2. The value for the Cs + basicity of 4-CF 3 benzoate published in a previous work 8 appears to be erroneous, as discussed in the The deviations between GB exp and GB calc are given in the fourth column. The respective affinities are given in the Supporting Information, Section S2.…”

Section: ■ Experimental Sectionmentioning

confidence: 98%

“…Most experiments were conducted in a way similar to studies on Cs + adducts. 8 Electrospray mass spectra were recorded on a Finnigan MAT (Thermo Electron, Courtaboeuf, France) LCQ DECA ion trap mass spectrometer, the source being operated under the following conditions: solution flow rate 3 μL•min −1 ; ESI voltage: −4.5 kV; capillary voltage and ion optic parameters: optimized by automatic tuning for each mixture of organic acid and alkali metal salts; capillary temperature: 200 °C; sheath gas: nitrogen. The m/z range was set between 50 and 2000.…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

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Alkali Metal Cations Bonding to Carboxylate Anions: Studies using Mass Spectrometry and Quantum Chemical Calculations

et al. 2020

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Data on the gas-phase energetics of anion/cation interactions are relatively scarce. In this work, gas-phase alkali metal cation basicity (AMCB) scales were established for a series of 15 benzoate ions XC6H4COO– with Li+, Na+, K+, Rb+, and Cs+ on the basis of mass spectrometry experiments and high-level calculations. A wide range of electron-donating and electron-withdrawing substituents were included in the study. The thermochemical values were calculated by ab initio methodologies and extrapolated to the complete basis set limit. For each metal cation, the experimental relative cation basicity values of the anions were established quantitatively by applying the Cooks’ kinetic method to the cation-bound heterodimers [(XC6H4COO–)M+(YC6H4COO–)]−, generated by electrospray ionization. The self-consistency of these AMCB scales was ascertained by multiple overlap of the individual relative basicities. In parallel, the proton gas-phase basicities (GBs) of the benzoate anions (gas-phase acidities of the respective benzoic acids) were calculated in order to compare the results of the theoretical method with known experimental GB values. The experimental and calculated GB values agree quite accurately (average absolute deviation = 3.2 kJ mol–1). The relative experimental AMCB scales and the absolute calculated AMCB scales are highly correlated, and the two sets agree by better than 4 kJ mol–1. It is also demonstrated that the five series of calculated AMCBs are highly correlated with the calculated GB.

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“…Kinetic Determination of Thermochemical Values for Gas-Phase Molecules difficult given that there is a lack of reference compounds with a known substrate affinity and, of course, we would not expect T eff to be constant throughout the range of complexes. An immediate option for smaller systems would be to use quantum computational techniques to approximate binding affinities for select reference compounds which have previously been used in conjunction with the kinetic method, 48 but because of the size of the present systems, the existence of many similar yet distinct molecular arrangements, this is not feasible.…”

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confidence: 99%

The Applicability of the Kinetic Method for Measuring Relative Affinities of Macromolecules for Polyatomic Substrates

Renaud

Mayer

2012

Eur J Mass Spectrom (Chichester)

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All rights reserved EUROPEAN JOURNAL OF MASS SPECTROMETRY Ion thermochemistry is a fundamental topic in ion chemistry and, as such, has been the topic of continuing interest since the early days of mass spectrometry. 1-3 Thermodynamic properties such as proton affinity, 4,5 metal ion affinity, 6,7 alkyl cation affinity 8,9 and electron affinity 10,11 have been explored by a variety of experimental and theoretical techniques. The most reliable are equilibrium methods, such as high-pressure mass spectrometry, which can directly yield the desired thermodynamic property of a molecule. Kinetics experiments performed under thermal conditions 12 can also produce reliable results, but these must be interpreted with great care. This is because such experiments directly measure the activation energy of a reaction which may, or may not, be the same as a reaction enthalpy due to the presence of a potential reverse energy barrier in the dissociation reaction. However, when these thermal experiments are not feasible, the "kinetic method," 13 as introduced by Cooks and Kruger in 1977 can, with care, produce reliable thermodynamic data. At

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A study of the cesium cation bonding to carboxylate anions by the kinetic method and quantum chemical calculations

Cited by 11 publications

References 38 publications

Monodisperse and Telechelic Polyethylenes Form Extended Chain Crystals with Ionic Layers

Monodisperse and Telechelic Polyethylenes Form Extended Chain Crystals with Ionic Layers

Alkali Metal Cations Bonding to Carboxylate Anions: Studies using Mass Spectrometry and Quantum Chemical Calculations

The Applicability of the Kinetic Method for Measuring Relative Affinities of Macromolecules for Polyatomic Substrates

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