A TRLFS Study on the Complexation of Cm<sup>III</sup> and Eu<sup>III</sup> with 2,6‐Bis(5,6‐dipropyl‐1,2,4‐triazin‐3‐yl)pyridine in Water/Methanol Mixture

Trumm, Sascha; Panak, Petra J.; Geist, Andreas; Fanghänel, Thomas

doi:10.1002/ejic.201000230

Cited by 59 publications

(137 citation statements)

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“…This results in a theoretical separation factor SF Cm III /Eu III = β′ 3,Cm III /β′ 3,Eu III ≈ 500, which is in the same order of magnitude as the values determined for n Pr-BTP (SF Cm III /Eu III = 320) 8,13 or C5-BPP (SF Cm III /Eu III ≈ 100). 21 Influence of a Lipophilic Anion Source.…”

Section: As Shown Insupporting

confidence: 72%

“…6-Cyano-2,2′-bipyridine 30 13,14 Et-BDP, 16 and n Pr-Tetrazine. 16 Fourier map calculations, as well as the magnitude of the residual electron densities, in each case were of no chemical significance.…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

“…54 This effect was also observed for other curium(III) complexes with a variety of aromatic nitrogendonor ligands. 13,24,51 For [Eu(N 4 bipy) 3 ], a fluorescence lifetime of 617 ± 48 μs is determined in EtOH and 592 ± 45 μs in EtOH/0.1 mol L −1 2-bromodecanoic acid (Supporting Information, Figure S11). The fluorescence lifetimes of [Eu(N 4 bipy) 3 ] in both solvents are significantly shorter than the lifetime of other BTP-type ligands in H 2 O 51 or H 2 O/MeOH, 13 indicating a significantly stronger fluorescence quenching by the HN 4 bipy ligand in contrast to nitrogen-donor ligands like n Pr-BTP or aq-BTP.…”

Section: As Shown Inmentioning

confidence: 99%

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6-(Tetrazol-5-yl)-2,2′-bipyridine: A Highly Selective Ligand for the Separation of Lanthanides(III) and Actinides(III)

et al. 2014

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The coordination structure in the solid state and solution complexation behavior of 6-(tetrazol-5-yl)-2,2'-bipyridine (HN4bipy) with samarium(III) was investigated as a model system for actinide(III)/lanthanide(III) separations. Two different solid 1:2 complexes, [Sm(N4bipy)2(OH)(H2O)2] (1) and [Sm(N4bipy)2(HCOO)(H2O)2] (2), were obtained from the reaction of samarium(III) nitrate with HN4bipy in isopropyl alcohol, resuspension in N,N-dimethylformamide (DMF), and slow crystallization. The formate anion coordinated to samarium in 2 is formed by decomposition of DMF to formic acid and dimethylamine. Time-resolved laser fluorescence spectroscopy (TRLFS) studies were performed with curium(III) and europium(III) by using HN4bipy as the ligand. Curium(III) is observed to form 1:2 and 1:3 complexes with increasing HN4bipy concentration; for europium(III), formation of 1:1 and 1:3 complexes is observed. Although the solid-state samarium complexes were confirmed as 1:2 species the 1:2 europium(III) solution complex in ethanol was not identified with TRLFS. The determined conditional stability constant for the 1:3 fully coordinated curium(III) complex species is more than 2 orders of magnitude higher than that for europium(III) (log β3[Cm(N4bipy)3] = 13.8 and log β3[Eu(N4bipy)3] = 11.1). The presence of added 2-bromodecanoic acid as a lipophilic anion source reduces the stability constant for formation of the 1:2 and 1:3 curium(III) complexes, but no ternary complexes were observed. The stability constants for the 1:3 metal ion-N4bipy complexes equate to a theoretical separation factor, SF(Cm(III)/Eu(III)) ≈ 500. However, the low solubility of the HN4bipy ligand in nonpolar solvents typically used in actinide-lanthanide liquid-liquid extractions prevents its use as a partitioning extractant until a more lipophilic HN4bipy-type ligand is developed.

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Section: As Shown Insupporting

confidence: 72%

Section: ■ Experimental Sectionmentioning

confidence: 99%

Section: As Shown Inmentioning

confidence: 99%

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6-(Tetrazol-5-yl)-2,2′-bipyridine: A Highly Selective Ligand for the Separation of Lanthanides(III) and Actinides(III)

et al. 2014

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“…[24][25][26] Information on the number and type of ligands as well as information on the complex geometry are provided by spectroscopic parameters like the position, shape and intensity of the emission bands. TRLFS has already been successfully used to study the coordination chemistry of Cm(III) and Eu (III) with BTP-and BTBP-type ligands in aqueous [14][15][16]27 and organic solutions. 28,29 Experimental section Chemicals All solvents were purchased by Merck KGaA and were used as supplied (UVASOL quality).…”

Section: Introductionmentioning

confidence: 99%

Influence of the solvent on the complexation of Cm(iii) and Eu(iii) with nPr–BTP studied by time-resolved laser fluorescence spectroscopy

et al. 2015

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The complexation of Cm(III) and Eu(III) with 2,6-bis(5,6-dipropyl-1,2,4-triazin-3-yl)pyridine (nPr-BTP) in methanol-water mixtures with varying water content is investigated by TRLFS. For both metal ions, the exclusive formation of the 1 : 3 complex is observed in each solvent mixture. Stability constants are determined by analysis of the fluorescence spectra. As a result, an immense influence of the water content is found. The stability constant of the [Cm(nPr-BTP) 3 ] 3+ complex increases by three orders of magnitude when the water content in methanol-water mixtures is reduced (log b 3 = 14.3 AE 0.1 at 50 vol% water content; log b 3 = 17.4 AE 0.4 at 5 vol% water content). Due to the preferential solvation of Cm(III) by water in methanol-water mixtures, the increase is moderate at water contents between 50 vol% and 20 vol% and becomes steeper at lower water contents. For the [Eu(nPr-BTP) 3 ] 3+ complex, an analogous evolution of the stability constant is observed (log b 3 = 12.0 AE 0.1 at 50 vol% water content; log b 3 = 14.7 AE 0.4 at 5 vol% water content). Therefore, the difference between the stability constants of the Cm(III) and Eu(III) 1 : 3 complexes is constant at all solvent mixtures investigated (Dlog b 3 = 2.3 AE 0.3) which means that the selectivity of the N-donor ligand is not influenced by the solvent.

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“…The complexation of Cm(III) and Eu(III) with a broad range of polydentate N-donor ligands has already been studied using TRLFS and reported. 27,36,32,28,34,29,30,37,38 Finally, liquid−liquid extraction tests were performed to study the extraction performance of BTTP. ■ EXPERIMENTAL SECTION Synthesis.…”

Section: ■ Introductionmentioning

confidence: 99%

A Complexation Study of 2,6-Bis(1-(p-tolyl)-1H-1,2,3-triazol-4-yl)pyridine Using Single-Crystal X-ray Diffraction and TRLFS

et al. 2015

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To develop a selective ligand for the separation of lanthanides(III) and actinides(III) the coordination chemistry of the chelating N-donor ligand 2,6-bis(1-(p-tolyl)-1H-1,2,3-triazol-4-yl)pyridine (BTTP) was investigated. The two isostructural lanthanide compounds [Ln(BTTP)3(OTf)3] (Ln = Eu (1), Sm (2); OTf = trifluoromethanesulfonate) were synthesized and fully characterized. The solid-state structures of both compounds were established by single-crystal X-ray diffraction. The complexation of Cm(III) and Eu(III) with BTTP in acetonitrile was studied using time-resolved laser fluorescence spectroscopy. With increasing BTTP concentration Cm(III) 1:2 and 1:3 complexes and Eu(III) 1:1 and 1:3 complexes are identified. The conditional stability constants of the 1:3 complex species with BTTP are log β3 = 14.0 for Cm(III) and log β3 = 10.3 for Eu(III). Both M(III) 1:3 complexes are prone to decomplexation with increasing acidity.

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A TRLFS Study on the Complexation of Cm^III and Eu^III with 2,6‐Bis(5,6‐dipropyl‐1,2,4‐triazin‐3‐yl)pyridine in Water/Methanol Mixture

Cited by 59 publications

References 29 publications

6-(Tetrazol-5-yl)-2,2′-bipyridine: A Highly Selective Ligand for the Separation of Lanthanides(III) and Actinides(III)

6-(Tetrazol-5-yl)-2,2′-bipyridine: A Highly Selective Ligand for the Separation of Lanthanides(III) and Actinides(III)

Influence of the solvent on the complexation of Cm(iii) and Eu(iii) with nPr–BTP studied by time-resolved laser fluorescence spectroscopy

A Complexation Study of 2,6-Bis(1-(p-tolyl)-1H-1,2,3-triazol-4-yl)pyridine Using Single-Crystal X-ray Diffraction and TRLFS

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A TRLFS Study on the Complexation of CmIII and EuIII with 2,6‐Bis(5,6‐dipropyl‐1,2,4‐triazin‐3‐yl)pyridine in Water/Methanol Mixture

Cited by 59 publications

References 29 publications

6-(Tetrazol-5-yl)-2,2′-bipyridine: A Highly Selective Ligand for the Separation of Lanthanides(III) and Actinides(III)

6-(Tetrazol-5-yl)-2,2′-bipyridine: A Highly Selective Ligand for the Separation of Lanthanides(III) and Actinides(III)

Influence of the solvent on the complexation of Cm(iii) and Eu(iii) with nPr–BTP studied by time-resolved laser fluorescence spectroscopy

A Complexation Study of 2,6-Bis(1-(p-tolyl)-1H-1,2,3-triazol-4-yl)pyridine Using Single-Crystal X-ray Diffraction and TRLFS

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A TRLFS Study on the Complexation of Cm^III and Eu^III with 2,6‐Bis(5,6‐dipropyl‐1,2,4‐triazin‐3‐yl)pyridine in Water/Methanol Mixture