Spectroscopic and Crystal Field Consequences of Fluoride Binding by [Yb⋅DTMA]3+ in Aqueous Solution. Issue 37 (27th July 2015)

• Record Type: Journal Article
• Authors: Blackburn, Octavia A.; Chilton, Nicholas F.; Keller, Katharina; Tait, Claudia E.; Myers, William K.; McInnes, Eric J. L.; Kenwright, Alan M.; Beer, Paul D.; Timmel, Christiane R.; Faulkner, Stephen
• Is Part Of: Angewandte Chemie international edition. Volume 54:Issue 37(2015)
• Page Start: 10783
• Page End: 10786
• Publication Date: 2015-07-27
• Subjects: Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201503421
• Languages: English
• ISSNs: 1433-7851

Abstract

<abstract abstract-type="main" xml:lang="en"> <title>Abstract</title> <p>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 (&lt;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 Yb^III 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.</p> </abstract>