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

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 con...

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Hauptverfasser: Bremer, Antje (VerfasserIn) , Müllich, Udo (VerfasserIn) , Geist, Andreas (VerfasserIn) , Panak, Petra (VerfasserIn)
Dokumenttyp: Article (Journal)
Sprache:Englisch
Veröffentlicht: 2015
In: New journal of chemistry
Year: 2014, Jahrgang: 39, Heft: 2, Pages: 1330-1338
ISSN:1369-9261
DOI:10.1039/C4NJ01900H
Online-Zugang:Verlag, lizenzpflichtig, Volltext: https://doi.org/10.1039/C4NJ01900H
Verlag, lizenzpflichtig, Volltext: https://pubs.rsc.org/en/content/articlelanding/2015/nj/c4nj01900h
Volltext
Verfasserangaben:Antje Bremer, Udo Müllich, 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-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 β3 = 14.3 ± 0.1 at 50 vol% water content; log β3 = 17.4 ± 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 β3 = 12.0 ± 0.1 at 50 vol% water content; log β3 = 14.7 ± 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 (Δlog β3 = 2.3 ± 0.3) which means that the selectivity of the N-donor ligand is not influenced by the solvent. 
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