Exploring Electronic Effects on the Partitioning of Actinides(III) from Lanthanides(III) using Functionalised Bis-triazinyl Phenanthroline Lig-ands

Research output: Contribution to journalArticle

  • External authors:
  • Alyn Edwards
  • Christoph Wagner
  • Andreas Geist
  • Neil Burton
  • Robin Pritchard
  • Petra J. Panak
  • Roger Whitehead
  • Laurence M. Harwood


The first examples of 4,7-disubstituted 2,9-bis(5,5,8,8-tetramethyl-5,6,7,8-tetrahydro-1,2,4-benzo-triazin-3-yl)-1,10-phenanthroline (CyMe4-BTPhen) ligands are reported herein. Evaluating the kinetics, selectivity and stoichiometry of acti-nide(III) and lanthanide(III) radiotracer extractions has provided a mechanistic insight into the extraction process. For the first time, it has been demonstrated that metal ion extraction kinetics can be modulated by backbone functionalisation and a promising new CHON compliant candidate ligand with enhanced metal ion extraction kinetics has been identified. The effects of 4,7-functionalisation on the equilibrium metal ion distribution ratios are far more pronounced than those of 5,6-functionalisation. The complexation of Cm(III) with two of the functionalised ligands was investigated by TRLFS and, at equilibrium, species of 1:2 [M:L] stoichiometry were observed exclusively. A direct correlation between the ELUMO-EHOMO energy gap and metal ion extraction potential is reported, with DFT studies reaffirming experimental findings.

Bibliographical metadata

Original languageEnglish
Pages (from-to)18102-18112
Number of pages11
JournalDalton Transactions
Early online date29 Jul 2016
StatePublished - 2016