Issue 45, 2016

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

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

Supplementary files

Article information

Article type
Paper
Submitted
20 Jun 2016
Accepted
28 Jul 2016
First published
29 Jul 2016

Dalton Trans., 2016,45, 18102-18112

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

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements