Radiation Stability of Cations in Ionic Liquids. 4. Task-Specific Antioxidant Cations for Nuclear Separations and Photolithography

Shkrob, Ilya A.; Marin, Timothy W.

doi:10.1021/jp408252n

Cited by 8 publications

(3 citation statements)

References 63 publications

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“…One is that many ionic liquids have a negligible vapor pressure, low flammability, and low toxicity and therefore can be used as stand-ins for conventional organic solvents. On the other hand, they also have been extensively studied for making chemical processes “greener”, as in the BASIL process or in the separation of lanthanides and nuclear waste disposal. − …”

Section: Introductionmentioning

confidence: 99%

Highly Luminescent Ionic Liquids Based on Complex Lanthanide Saccharinates

Tang

Mudring

2019

Inorg. Chem.

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Four strongly luminescent ionic liquids with complex lanthanide saccharinate anions, [C4mim]3[Eu(Sac)6(H2O)2] (1), {C4mpy}5{[Ln(Sac)6(H2O)2][Ln(Sac)5(H2O)3]}{(H2O)2(CH3CN)2} (Ln = Sm for 2a; Ln = Eu for 2b), and [C4mpy]3[Eu(Sac)6][CH3CN] (3) (C4mim = 1-butyl-3-methylimidazolium; C4mpy = N-butyl-4-methylpyridinium; Sac = saccharinate), have been obtained by reacting the ionic liquids 1-butyl-3-methylimidazolium saccharinate, [C4mim][Sac], and N-butyl-4-methylpyridinium saccharinate, [C4mpy][Sac], with the respective lanthanide saccharinates. Single-crystal X-ray diffraction analyses reveal the respective lanthanide center to be six- or eight-coordinated by five or six saccharinate anions and two or three aqua ligands in the cases of 1 and 2 when lanthanide saccharinated hydrate was employed as the starting material. Coordination of water to the lanthanide can be avoided when using the anhydrous lanthanide saccharinate as shown by the structure of 3. Using a co-solvent, acetonitrile, to facilitate the reaction led to incorporation of solvent molecules into the crystal structure of the final materials (2 and 3). Differential scanning calorimetry analyses reveal that 1 is an ionic liquid whereas 2 and 3 are low-temperature molten salts. The three europium(III)-containing compounds (1, 2b, and 3) all show characteristic intense red emissions of Eu(III) upon excitation into levels of the saccharinate ligands (321 nm) or Eu(III) (393 nm). At room temperature, the decay times of 1 and 2b are all ∼0.5 ms, whereas the decay time of 3 amounts to 3.85 ms due to removal of aqua ligands in the first coordination sphere; accordingly, the quantum efficiencies of 1, 2b, and 3 were determined to be 15.9%, 22.95%, and 57.75%, respectively. The CIE chromaticity coordinates for all Eu compounds are in the red region and approach the NTSC standard CIE values when the temperature is increased. Sm(III)-containing compound 2a shows characteristic Sm(III) emission peaks. As expected, the CIE coordinates of samarium compound 2a fall in the orange-red region.

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Section: Introductionmentioning

confidence: 99%

Highly Luminescent Ionic Liquids Based on Complex Lanthanide Saccharinates

Tang

Mudring

2019

Inorg. Chem.

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“…In nuclear applications, the radiation stability of an extraction system is important in assessing potential practical applications, and it should be assessed carefully. − Existing studies of radiation effects focused mainly on pure RTILs under γ-irradiation, − and the water-soluble radiolytic products of NTf 2 -based ionic liquids were identified. , Minimal work has been carried out on the radiolysis of TSILs; for example, Shkrob et al used electron paramagnetic resonance spectroscopy to study the radiation stability of cations of TSILs. Antioxidant organic cation deprotonation from the excited state is reversible and leads to minimal TSIL damage.…”

Section: Introductionmentioning

confidence: 99%

Radiation Effect of Carboxyl-Functionalized Task-Specific Ionic Liquids on UO₂²⁺ Removal: Experimental Study with DFT Validation

Chen

Wang

et al. 2017

J. Phys. Chem. B

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Experimental study with DFT validation on the effect of radiation on 1-carboxymethyl-3-methylimidazolium bis(trifluoromethylsulfonyl) imide ([HOOCCHMIM][NTf]) as a solvent and extractant in rapid homogeneous extraction of UO was performed for the first time. The radiolytic products of the anions and cations of [HOOCCHMIM][NTf] were identified by F NMR and high-resolution ESI-MS, respectively, and they were attributed to a decrease in UO partitioning. Experimental study with DFT validation for complexing reactions between [HOOCCHMIM][NTf] and radiolytic products proved that F competition was one of the main reasons for the decrease in UO partitioning. However, UO partitioning in irradiated [HOOCCHMIM][NTf] can largely be recovered after thorough water washing because of the removal of radiolytic products of [NTf].

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“…In a series of publications from our two laboratories − we aimed to learn how structural variations in organic cations affect the radiation stability of ILs. In Part 5 of this series, we focus on functional modifications for the simplest of organic cations: tetraalkylammonium (Scheme ) ions.…”

Section: Introductionmentioning

confidence: 99%

Radiation Stability of Cations in Ionic Liquids. 5. Task-Specific Ionic Liquids Consisting of Biocompatible Cations and the Puzzle of Radiation Hypersensitivity

et al. 2014

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In 1953, an accidental discovery by Melvin Calvin and co-workers provided the first example of a solid (the α-polymorph of choline chloride) showing hypersensitivity to ionizing radiation: under certain conditions, the radiolytic yield of decomposition approached 5 × 10(4) per 100 eV (which is 4 orders of magnitude greater than usual values), suggesting an uncommonly efficient radiation-induced chain reaction. Twenty years later, the still-accepted mechanism for this rare condition was suggested by Martyn Symons, but no validation for this mechanism has been supplied. Meanwhile, ionic liquids and deep eutectic mixtures that are based on choline, betainium, and other derivitized natural amino compounds are presently finding an increasing number of applications as diluents in nuclear separations, where the constituent ions are exposed to ionizing radiation that is emitted by decaying radionuclides. Thus, the systems that are compositionally similar to radiation hypersensitive solids are being considered for use in high radiation fields, where this property is particularly undesirable! In Part 5 of this series on organic cations, we revisit the phenomenon of radiation hypersensitivity and explore mechanistic aspects of radiation-induced reactions involving this class of task-specific, biocompatible, functionalized cations, both in ionic liquids and in reference crystalline compounds. We demonstrate that Symons' mechanism needs certain revisions and rethinking, and suggest its modification. Our reconsideration suggests that there cannot be conditions leading to hypersensitivity in ionic liquids.

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Radiation Stability of Cations in Ionic Liquids. 4. Task-Specific Antioxidant Cations for Nuclear Separations and Photolithography

Cited by 8 publications

References 63 publications

Highly Luminescent Ionic Liquids Based on Complex Lanthanide Saccharinates

Highly Luminescent Ionic Liquids Based on Complex Lanthanide Saccharinates

Radiation Effect of Carboxyl-Functionalized Task-Specific Ionic Liquids on UO₂²⁺ Removal: Experimental Study with DFT Validation

Radiation Stability of Cations in Ionic Liquids. 5. Task-Specific Ionic Liquids Consisting of Biocompatible Cations and the Puzzle of Radiation Hypersensitivity

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Radiation Stability of Cations in Ionic Liquids. 4. Task-Specific Antioxidant Cations for Nuclear Separations and Photolithography

Cited by 8 publications

References 63 publications

Highly Luminescent Ionic Liquids Based on Complex Lanthanide Saccharinates

Highly Luminescent Ionic Liquids Based on Complex Lanthanide Saccharinates

Radiation Effect of Carboxyl-Functionalized Task-Specific Ionic Liquids on UO22+ Removal: Experimental Study with DFT Validation

Radiation Stability of Cations in Ionic Liquids. 5. Task-Specific Ionic Liquids Consisting of Biocompatible Cations and the Puzzle of Radiation Hypersensitivity

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Radiation Effect of Carboxyl-Functionalized Task-Specific Ionic Liquids on UO₂²⁺ Removal: Experimental Study with DFT Validation