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Issue 45, 2016
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Exploring electronic effects on the partitioning of actinides(III) from lanthanides(III) using functionalised bis-triazinyl phenanthroline ligands

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Abstract

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 actinide(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 ELUMOEHOMO energy gap and metal ion extraction potential is reported, with DFT studies reaffirming experimental findings.

Graphical abstract: Exploring electronic effects on the partitioning of actinides(iii) from lanthanides(iii) using functionalised bis-triazinyl phenanthroline ligands

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Publication details

The article was received on 20 Jun 2016, accepted on 28 Jul 2016 and first published on 29 Jul 2016


Article type: Paper
DOI: 10.1039/C6DT02474B
Citation: Dalton Trans., 2016,45, 18102-18112
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    Exploring electronic effects on the partitioning of actinides(III) from lanthanides(III) using functionalised bis-triazinyl phenanthroline ligands

    A. C. Edwards, C. Wagner, A. Geist, N. A. Burton, C. A. Sharrad, R. W. Adams, R. G. Pritchard, P. J. Panak, R. C. Whitehead and L. M. Harwood, Dalton Trans., 2016, 45, 18102
    DOI: 10.1039/C6DT02474B

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