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NMR and TRLFS studies of Ln(III) and An(III) C5-BPP complexes

Adam, C. 1; Beele, B. B. 1; Geist, A. ORCID iD icon 1; Müllich, U. 1; Kaden, P. 1; Panak, P. J. 1
1 Institut für Nukleare Entsorgung (INE), Karlsruher Institut für Technologie (KIT)


C5-BPP is a highly efficient N-donor ligand for the separation of trivalent actinides, An(III), from trivalent lanthanides, Ln(III). The molecular origin of the selectivity of C5-BPP and many other N-donor ligands of the BTP-type is still not entirely understood. We present here the first NMR studies on C5-BPP Ln(III) and An(III) complexes. C5-BPP is synthesized with 10% 15N labeling and characterized by NMR and LIFDI-MS methods. 15N NMR spectroscopy gives a detailed insight into the bonding of C5-BPP with lanthanides and Am(III) as a representative for trivalent actinide cations, revealing significant differences in 15N chemical shift for coordinating nitrogen atoms compared to Ln(III) complexes. The temperature dependence of NMR chemical shifts observed for the Am(III) complex indicates a weak paramagnetism. This as well as the observed large chemical shift for coordinating nitrogen atoms show that metal–ligand bonding in Am(C5-BPP)3 has a larger share of covalence than in lanthanide complexes, confirming earlier studies. The Am(C5-BPP)3 NMR sample is furthermore spiked with Cm(III) and characterized by time-resolved laser fluorescence spectroscopy (TRLFS), yielding important information on the speciation of trace amounts of minor complex species.

Verlagsausgabe §
DOI: 10.5445/IR/110099814
Veröffentlicht am 19.10.2018
DOI: 10.1039/C4SC03103B
Zitationen: 38
Web of Science
Zitationen: 37
Zitationen: 39
Cover der Publikation
Zugehörige Institution(en) am KIT Institut für Nukleare Entsorgung (INE)
Publikationstyp Zeitschriftenaufsatz
Publikationsjahr 2015
Sprache Englisch
Identifikator ISSN: 2041-6520, 2041-6539
KITopen-ID: 110099814
HGF-Programm 32.01.11 (POF III, LK 01) Extraktions- und Koordinationschemie der Actiniden
Erschienen in Chemical science
Verlag Royal Society of Chemistry (RSC)
Band 6
Seiten 1548-1561
Nachgewiesen in Scopus
Web of Science
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