2,6-Bis(5,6-diisopropyl-1,2,4-triazin-3-yl)pyridine: a highly selective N-donor ligand studied by TRLFS, liquid-liquid extraction and molecular dynamics
The complexation of Cm(III) and Eu(III) with 2,6-bis(5,6-di-i-propyl-1,2,4-triazin-3-yl)-pyridine (iPr-BTP) is studied in methanol : water (1 : 1, vol) by time-resolved laser-induced fluorescence spectroscopy (TRLFS). With increasing ligand concentration [Cm(iPr-BTP)3]3+ and [Eu(iPr-BTP)3]3+ are for...
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| Hauptverfasser: | , , , , , , , , , , |
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| Dokumenttyp: | Article (Journal) |
| Sprache: | Englisch |
| Veröffentlicht: |
14th November 2016
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| In: |
New journal of chemistry
Year: 2016, Jahrgang: 40, Heft: 12, Pages: 10389-10397 |
| ISSN: | 1369-9261 |
| DOI: | 10.1039/C6NJ02657E |
| Online-Zugang: | Verlag, lizenzpflichtig, Volltext: https://doi.org/10.1039/C6NJ02657E Verlag, lizenzpflichtig, Volltext: https://pubs.rsc.org/en/content/articlelanding/2016/nj/c6nj02657e 
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| Verfasserangaben: | Björn B. Beele, Andrej Skerencak-Frech, Arnulf Stein, Michael Trumm, Andreas Wilden, Steve Lange, Giuseppe Modolo, Udo Müllich, Bernd Schimmelpfennig, Andreas Geist and Petra J. Panak |
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| 245 | 1 | 0 | |a 2,6-Bis(5,6-diisopropyl-1,2,4-triazin-3-yl)pyridine |b a highly selective N-donor ligand studied by TRLFS, liquid-liquid extraction and molecular dynamics |c Björn B. Beele, Andrej Skerencak-Frech, Arnulf Stein, Michael Trumm, Andreas Wilden, Steve Lange, Giuseppe Modolo, Udo Müllich, Bernd Schimmelpfennig, Andreas Geist and Petra J. Panak |
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| 520 | |a The complexation of Cm(III) and Eu(III) with 2,6-bis(5,6-di-i-propyl-1,2,4-triazin-3-yl)-pyridine (iPr-BTP) is studied in methanol : water (1 : 1, vol) by time-resolved laser-induced fluorescence spectroscopy (TRLFS). With increasing ligand concentration [Cm(iPr-BTP)3]3+ and [Eu(iPr-BTP)3]3+ are formed, respectively. Stability constants of log β3′([Cm(iPr-BTP)3]3+) = 16.3 ± 0.3 and log β3′([Eu(iPr-BTP)3]3+) = 14.9 ± 0.3 are determined. Thermodynamic data of the complexation reactions is obtained in a temperature range of 20-60 °C. The complexation of iPr-BTP with both metal ions is exothermic (Cm(III): ΔrH3′ = −(64.1 ± 3.0) kJ mol−1; Eu(III): ΔrH3′ = −(42.6 ± 2.0) kJ mol−1). The reaction entropy for the formation of [Eu(iPr-BTP)3]3+ is higher compared to the Cm(III) complex (Cm(III): ΔrS3′ = (96.5 ± 6.5) J mol−1 K−1; Eu(III): ΔrS3′ = (136.0 ± 15.2) J mol−1 K−1). Different complexation entropies for the formation of [Cm(iPr-BTP)3] and [Cm(nPr-BTP)3] are explained by molecular dynamics simulations. Results from liquid-liquid extraction tests confirm the ligand's peculiar extraction kinetics observed in previous studies and link them to the thermodynamic data. | ||
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