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| 2. |
- Bousrez, Guillaume, et al.
(författare)
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Ready Access to Anhydrous Anionic Lanthanide Acetates by Using Imidazolium Acetate Ionic Liquids as the Reaction Medium
- 2021
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Ingår i: Chemistry - A European Journal. - : Wiley. - 0947-6539 .- 1521-3765. ; 27:52, s. 13181-13189
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Tidskriftsartikel (refereegranskat)abstract
- Access to lanthanide acetate coordination compounds is challenged by the tendency of lanthanides to coordinate water and the plethora of acetate coordination modes. A straightforward, reproducible synthetic procedure by treating lanthanide chloride hydrates with defined ratios of the ionic liquid (IL) 1-ethyl-3-methylimidazolium acetate ([C(2)mim][OAc]) has been developed. This reaction pathway leads to two isostructural crystalline anhydrous coordination complexes, the polymeric [C(2)mim](n)[{Ln(2)(OAc)(7)}(n)] and the dimeric [C(2)mim](2)[Ln(2)(OAc)(8)], based on the ion size and the ratio of IL used. A reaction with an IL : Ln-salt ratio of 5 : 1, where Ln=Nd, Sm, and Gd, led exclusively to the polymer, whilst for the heaviest lanthanides (Dy-Lu) the dimer was observed. Reaction with Eu and Tb resulted in a mixture of both polymeric and dimeric forms. When the amount of IL and/or the size of the cation was increased, the reaction led to only the dimeric compound for all the lanthanide series. Crystallographic analyses of the resulting salts revealed three different types of metal-acetate coordination modes where eta(2)mu kappa(2) is the most represented in both structure types.
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| 3. |
- Smetana, Volodymyr, et al.
(författare)
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Synthesis of Anhydrous Acetates for the Components of Nuclear Fuel Recycling in Dialkylimidazolium Acetate Ionic Liquids
- 2020
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Ingår i: Inorganic Chemistry. - : American Chemical Society (ACS). - 0020-1669 .- 1520-510X. ; 59:1, s. 818-828
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Tidskriftsartikel (refereegranskat)abstract
- A series of anhydrous acetate salts with uranium {[C(2)C(1)im][UO2(OAc)(3)] (1), [C(2)C(2)im][UO2(OAc)(3)] (2), and [C(4)C(1)im][UO2(OAc)(3)] (3)}, lanthanides {[C(2)C(2)im](2) [La(OAc)(5)] (4) and [C(2)C(1)im](2) [Nd(OAc)(5)] (5)}, and strontium {[C(2)C(1)im](n)[Sr-(OAc)(3)](n) (6)} (where C(2)C(1)im = 1-ethyl-3-methylimidazolium, C2C2 im = 1,3-diethylimidazolium, C4C1 im = 1-butyl-3-methylimidazolium, and OAc = acetate) have been prepared and structurally characterized. Both lanthanides and strontium are common components of the nuclear fuel waste, and their separation from uranium is an important but still challenging task. A new synthetic approach with dialkylimidazolium acetate ionic liquids (ILs) as the solvent has been developed for the direct synthesis of homoleptic acetates from the corresponding hydrates and, unexpectedly, hardly soluble f-element oxides. Although the group of characterized compounds shows perfect structural variability, all actinide and lanthanide metal ions form monomeric complex anions where the metal cation coordinates to five ligands including two oxygen atoms in the case of uranium, as is commonly observed for uranyl compounds. Crystallographic analyses revealed that the complex [UO2(OAc)(3)](-) anions possess rather standard D-3h symmetry featuring a hexagonal-bipyramidal coordination environment, while the lanthanide anions [Ln(OAc)(5)](2-) are fully asymmetric and the Ln(3+) cations are 10-coordinated in the form of a distorted bicapped tetragonal antiprism. This is the first report of lanthanide ions coordinated in this fashion. For Sr2+, 9-fold coordination through oxygen atoms in the form of a strongly distorted tricapped trigonal prism is observed. The crystallization of anhydrous, homoleptic, anionic acetate complexes from such a large variety of different metal salts appears to be due to the properties of dialkylimidazolium acetate ILs themselves, including enhanced basicity from the high concentration of free anions and their greater affinity for hydrogen-bonding solutes relative to metal cations.
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| 4. |
- Tang, Si-Fu, et al.
(författare)
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Forcing Dicyanamide Coordination to f-Elements by Dissolution in Dicyanamide-Based Ionic Liquids
- 2020
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Ingår i: Inorganic Chemistry. - : American Chemical Society (ACS). - 0020-1669 .- 1520-510X. ; 59:10, s. 7227-7237
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Tidskriftsartikel (refereegranskat)abstract
- A robust general route to lanthanide dicyanamide (DCA(-)) complexes has been developed where f-element salts are dissolved in DCA(-)-based ionic liquids (ILs) directly or formed in situ, forcing coordination of these normally weakly coordinating soft N-donor anions, even in an ambient, non-moisture-excluding environment. A series of lanthanide complexes [C(2)mim][Ln(DCA)(4)(H2O)(4)] (C(2)mim = 1-ethyl-3-methylimidazolium; Ln = La, Nd, Eu, Tb, Dy, and Yb) and [C(2)mim](3n)[La(OH2)(4) (mu(2)-DCA)(4)](n)[La(OH2)(2)(mu(3)-DCA)(3)(mu(2)-DCA)(4)](2n)(Cl)(4n) were crystallized under a variety of conditions using this methodology and structurally characterized using single crystal X-ray diffraction. Although not all examples were isostructural, the dominant feature across the series was the presence of [Ln(DCA)(4)(H2O)(4)](-) anionic nodes with all terminal DCA(-) ligands accepting hydrogen bonds from the coordinated water molecules forming a 3D metal organic framework. To determine if any structural clues might aid in the further development of the synthetic methodology, the metal-free IL [C(1)mim][DCA] (C(1)mim = 1,3-dimethylimidazolium), a room-temperature solid, crystalline analogue of the reaction IL, which is liquid at room temperature, was also prepared and structurally characterized. The ready isolation of these compounds allowed us to begin an investigation of the physical properties such as the luminescence at room and low temperatures for the Eu, Tb, and Dy representatives.
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| 5. |
- Tang, Si-Fu, et al.
(författare)
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Highly Luminescent Ionic Liquids Based on Complex Lanthanide Saccharinates
- 2019
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Ingår i: Inorganic Chemistry. - : American Chemical Society (ACS). - 0020-1669 .- 1520-510X. ; 58:17, s. 11569-11578
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Tidskriftsartikel (refereegranskat)abstract
- Four strongly luminescent ionic liquids with complex lanthanide saccharinate anions, [C(4)mim](3)[Eu-Sac)(6)(H2O)(2)] (1), {C(4)mpy}(5){[Ln-(Sac)(6)(H2O)(2)][Ln-(Sac)(5)(H2O)(3)]}{(H2O)(2)(CH3CN)(2)} (Ln = Sm for 2a; Ln = Eu for 2b), and [C(4)mpy](3)[Eu(Sac)(6)][CH3CN] (3) (C(4)mim = 1-butyl-3-methylimidazolium; C(4)mpy = N-butyl-4-methylpyridinium; Sac = saccharinate), have been obtained by reacting the ionic liquids 1-butyl-3-methylimidazolium saccharinate, [C(4)mim] [Sac], and N-butyl-4-methylpyridinium saccharinate, [C(4)mpy] [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 similar to 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 orangered region.
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