Using Remote Substituents to Control Solution Structure and Anion Binding in Lanthanide Complexes

Tropiano, Manuel; Blackburn, Octavia A.; Tilney, James A.; Hill, Leila R.; Placidi, Matteo P.; Aarons, Rebecca J.; Sykes, Daniel; Jones, Michael W.; Kenwright, Alan M.; Snaith, John S.; Sørensen, Thomas Just; Faulkner, Stephen

doi:10.1002/chem.201303183

Using Remote Substituents to Control Solution Structure and Anion Binding in Lanthanide Complexes

Tropiano, Manuel; Blackburn, Octavia A.; Tilney, James A.; Hill, Leila R.; Placidi, Matteo P.; Aarons, Rebecca J.; Sykes, Daniel; Jones, Michael W.; Kenwright, Alan M.; Snaith, John S.; Sørensen, Thomas Just; Faulkner, Stephen

Authors

Manuel Tropiano

Octavia A. Blackburn

James A. Tilney

Leila R. Hill

Matteo P. Placidi

Rebecca J. Aarons

Daniel Sykes

Michael W. Jones

Alan M. Kenwright

John S. Snaith

Thomas Just Sørensen

Stephen Faulkner

Abstract

A study of the anion-binding properties of three structurally related lanthanide complexes, which all contain chemically identical anion-binding motifs, has revealed dramatic differences in their anion affinity. These arise as a consequence of changes in the substitution pattern on the periphery of the molecule, at a substantial distance from the binding pocket. Herein, we explore these remote substituent effects and explain the observed behaviour through discussion of the way in which remote substituents can influence and control the global structure of a molecule through their demands upon conformational space. Peripheral modifications to a binuclear lanthanide motif derived from α,α′-bis(DO3 Ayl)-m-xylene are shown to result in dramatic changes to the binding constant for isophthalate. In this system, the parent compound displays considerable conformational flexibility, yet can be assumed to bind to isophthalate through a well-defined conformer. Addition of steric bulk remote from the binding site restricts conformational mobility, giving rise to an increase in binding constant on entropic grounds as long as the ideal binding conformation is not excluded from the available range of conformers.

Citation

Tropiano, M., Blackburn, O. A., Tilney, J. A., Hill, L. R., Placidi, M. P., Aarons, R. J., …Faulkner, S. (2013). Using Remote Substituents to Control Solution Structure and Anion Binding in Lanthanide Complexes. Chemistry - A European Journal, 19(49), 16566-16571. https://doi.org/10.1002/chem.201303183

Journal Article Type	Article
Publication Date	Dec 2, 2013
Deposit Date	Nov 20, 2014
Publicly Available Date	Nov 21, 2014
Journal	Chemistry - A European Journal
Print ISSN	0947-6539
Electronic ISSN	1521-3765
Publisher	Wiley
Peer Reviewed	Peer Reviewed
Volume	19
Issue	49
Pages	16566-16571
DOI	https://doi.org/10.1002/chem.201303183
Keywords	Anions, Conformational space, Lanthanides, Luminescence, Remote effects.

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Copyright Statement
This is the peer reviewed version of the following article: Tropiano, M., Blackburn, O. A., Tilney, J. A., Hill, L. R., Placidi, M. P., Aarons, R. J., Sykes, D., Jones, M. W., Kenwright, A. M., Snaith, J. S., Sørensen, T. J. and Faulkner, S. (2013), Using Remote Substituents to Control Solution Structure and Anion Binding in Lanthanide Complexes. Chemistry - a European journal, 19 (49): 16566-16571, which has been published in final form at http://dx.doi.org/10.1002/chem.201303183. This article may be used for non-commercial purposes in accordance With Wiley-VCH Terms and Conditions for self-archiving.