Spectroscopic and Crystal Field Consequences of Fluoride Binding by [Yb⋅DTMA](3+) in Aqueous Solution

Blackburn, O.A.; Chilton, N.F.; Keller, K.; Tait, C.E.; Myers, W.K.; McInnes, E.J.; Kenwright, A.M.; Beer, P.D.; Timmel, C.R.; Faulkner, S.

doi:10.1002/anie.201503421

Spectroscopic and Crystal Field Consequences of Fluoride Binding by [Yb⋅DTMA](3+) in Aqueous Solution

Blackburn, O.A.; Chilton, N.F.; Keller, K.; Tait, C.E.; Myers, W.K.; McInnes, E.J.; Kenwright, A.M.; Beer, P.D.; Timmel, C.R.; Faulkner, S.

Authors

O.A. Blackburn

N.F. Chilton

K. Keller

C.E. Tait

W.K. Myers

E.J. McInnes

A.M. Kenwright

P.D. Beer

C.R. Timmel

S. Faulkner

Abstract

Yb⋅DTMA forms a ternary complex with fluoride in aqueous solution by displacement of a bound solvent molecule from the lanthanide ion. [Yb⋅DTMA⋅F]2+ and [Yb⋅DTMA⋅OH2]3+ are in slow exchange on the relevant NMR timescale (<2000 s−1), and profound differences are observed in their respective NMR and EPR spectra of these species. The observed differences can be explained by drastic modification of the ligand field states due to the fluoride binding. This changes the magnetic anisotropy of the YbIII ground state from easy-axis to easy-plane type, and this change is easily detected in the observed magnetic anisotropy despite thermal population of more than just the ground state. The spectroscopic consequences of such drastic changes to the ligand field represent important new opportunities in developing fluoride-responsive complexes and contrast agents.

Citation

Blackburn, O., Chilton, N., Keller, K., Tait, C., Myers, W., McInnes, E., …Faulkner, S. (2015). Spectroscopic and Crystal Field Consequences of Fluoride Binding by [Yb⋅DTMA](3+) in Aqueous Solution. Angewandte Chemie International Edition, 54(37), 10783-10786. https://doi.org/10.1002/anie.201503421

Journal Article Type	Article
Online Publication Date	Jul 27, 2015
Publication Date	Sep 7, 2015
Deposit Date	Aug 10, 2015
Publicly Available Date	Jul 27, 2016
Journal	Angewandte Chemie International Edition
Print ISSN	1433-7851
Electronic ISSN	1521-3773
Publisher	Wiley
Peer Reviewed	Peer Reviewed
Volume	54
Issue	37
Pages	10783-10786
DOI	https://doi.org/10.1002/anie.201503421
Keywords	Anion coordination, Lanthanide, Magnetic anisotropy, NMR spectroscopy, Spectroscopic methods.

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Copyright Statement
This is the peer reviewed version of the following article: Blackburn, O. A., Chilton, N. F., Keller, K., Tait, C. E., Myers, W. K., McInnes, E. J. L., Kenwright, A. M., Beer, P. D., Timmel, C. R. and Faulkner, S. (2015), Spectroscopic and Crystal Field Consequences of Fluoride Binding by [Yb⋅DTMA]3+ in Aqueous Solution. Angewandte Chemie International Edition, 54(37): 10783-10786, which has been published in final form at http://dx.doi.org/10.1002/anie.201503421. This article may be used for non-commercial purposes in accordance With Wiley-VCH Terms and Conditions for self-archiving.