Substituent effects on fluoride binding by lanthanide complexes of DOTA-tetraamides

Blackburn, Octavia A.; Routledge, Jack D.; Jennings, Laura B.; Rees, Nicholas H.; Kenwright, Alan M.; Beer, Paul D.; Faulkner, Stephen

doi:10.1039/c5dt04349b

Substituent effects on fluoride binding by lanthanide complexes of DOTA-tetraamides

Blackburn, Octavia A.; Routledge, Jack D.; Jennings, Laura B.; Rees, Nicholas H.; Kenwright, Alan M.; Beer, Paul D.; Faulkner, Stephen

Authors

Octavia A. Blackburn

Jack D. Routledge

Laura B. Jennings

Nicholas H. Rees

Alan M. Kenwright

Paul D. Beer

Stephen Faulkner

Abstract

Fluoride binding by a series of europium and ytterbium complexes of DOTA-tetraamide ligands derived from primary, secondary and tertiary amides has been studied by NMR and luminescence spectroscopies. In all the systems studied, fluoride binding results in a change in the nature of the magnetic anisotropy at the metal centre from an easy axis, to an easy plane anisotropy. This results in reversal of the peaks in the NMR spectra, and in changes to the fine structure of the luminescence spectra. Furthermore, changes to the periphery of the binding cavity are implicated in determining the affinity constant for fluoride. There are clear differences in the entropic contribution to the free energy of activation between systems with benzylic amides and those with methylamides.

Citation

Blackburn, O. A., Routledge, J. D., Jennings, L. B., Rees, N. H., Kenwright, A. M., Beer, P. D., & Faulkner, S. (2016). Substituent effects on fluoride binding by lanthanide complexes of DOTA-tetraamides. Dalton Transactions, 45(7), 3070-3077. https://doi.org/10.1039/c5dt04349b

Journal Article Type	Article
Acceptance Date	Jan 4, 2016
Online Publication Date	Jan 4, 2016
Publication Date	Feb 21, 2016
Deposit Date	Jan 14, 2016
Publicly Available Date	Jan 4, 2017
Journal	Dalton Transactions
Print ISSN	1477-9226
Electronic ISSN	1477-9234
Publisher	Royal Society of Chemistry
Peer Reviewed	Peer Reviewed
Volume	45
Issue	7
Pages	3070-3077
DOI	https://doi.org/10.1039/c5dt04349b