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Exploring the Subtle Effect of Aliphatic Ring Size on Minor Actinide-Extraction Properties and Metal Ion Speciation in Bis-1,2,4-Triazine Ligands

Lookup NU author(s): Dr Andrey Zaytsev, Rachel Bulmer, Dr Paul Waddell



This work is licensed under a Creative Commons Attribution 4.0 International License (CC BY 4.0).


© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim. The synthesis and evaluation of three novel bis-1,2,4-triazine ligands containing five-membered aliphatic rings are reported. Compared to the more hydrophobic ligands 1–3 containing six-membered aliphatic rings, the distribution ratios for relevant f-block metal ions were approximately one order of magnitude lower in each case. Ligand 10 showed an efficient, selective and rapid separation of AmIII and CmIII from nitric acid. The speciation of the ligands with trivalent f-block metal ions was probed using NMR titrations and competition experiments, time-resolved laser fluorescence spectroscopy and X-ray crystallography. While the tetradentate ligands 8 and 10 formed LnIII complexes of the same stoichiometry as their more hydrophobic analogues 2 and 3, significant differences in speciation were observed between the two classes of ligand, with a lower percentage of the extracted 1:2 complexes being formed for ligands 8 and 10. The structures of the solid state 1:1 and 1:2 complexes formed by 8 and 10 with YIII, LuIII and PrIII are very similar to those formed by 2 and 3 with LnIII. Ligand 10 forms CmIII and EuIII 1:2 complexes that are thermodynamically less stable than those formed by ligand 3, suggesting that less hydrophobic ligands form less stable AnIII complexes. Thus, it has been shown for the first time how tuning the cyclic aliphatic part of these ligands leads to subtle changes in their metal ion speciation, complex stability and metal extraction affinity.

Publication metadata

Author(s): Zaytsev AV, Bulmer R, Kozhevnikov VN, Sims M, Modolo G, Wilden A, Waddell PG, Geist A, Panak PJ, Wessling P, Lewis FW

Publication type: Article

Publication status: Published

Journal: Chemistry - A European Journal

Year: 2020

Volume: 26

Issue: 2

Pages: 428-437

Print publication date: 07/01/2020

Online publication date: 05/09/2019

Acceptance date: 12/08/2019

Date deposited: 18/11/2019

ISSN (print): 0947-6539

ISSN (electronic): 1521-3765

Publisher: Wiley-VCH Verlag


DOI: 10.1002/chem.201903685


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