title: Spectroscopic and Crystal Field Consequences of Fluoride Binding by [Yb⋅DTMA]3+in Aqueous Solution.
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 YbIIIground 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.
authors.affiliation: Chemistry Research Laboratory, University of Oxford, Mansfield Road, Oxford OX1 3TA (UK).
authors.forename: Octavia A
authors.initials: OA
authors.lastname: Blackburn
authors.affiliation: School of Chemistry, and Photon Science Institute, University of Manchester, Oxford Road, Manchester M13 9PL (UK).
authors.forename: Nicholas F
authors.initials: NF
authors.lastname: Chilton
authors.affiliation: Centre for Advanced ESR (CÆSR), Inorganic Chemistry Laboratory, University of Oxford, South Parks Road, Oxford, OX1 3QR (UK).
authors.forename: Katharina
authors.initials: K
authors.lastname: Keller
authors.affiliation: Centre for Advanced ESR (CÆSR), Inorganic Chemistry Laboratory, University of Oxford, South Parks Road, Oxford, OX1 3QR (UK).
authors.forename: Claudia E
authors.initials: CE
authors.lastname: Tait
authors.affiliation: Centre for Advanced ESR (CÆSR), Inorganic Chemistry Laboratory, University of Oxford, South Parks Road, Oxford, OX1 3QR (UK).
authors.forename: William K
authors.initials: WK
authors.lastname: Myers
authors.affiliation: School of Chemistry, and Photon Science Institute, University of Manchester, Oxford Road, Manchester M13 9PL (UK).
authors.forename: Eric J L
authors.initials: EJ
authors.lastname: McInnes
authors.affiliation: Department of Chemistry, University of Durham, South Road, Durham DH1 3LE (UK).
authors.forename: Alan M
authors.initials: AM
authors.lastname: Kenwright
authors.affiliation: Chemistry Research Laboratory, University of Oxford, Mansfield Road, Oxford OX1 3TA (UK).
authors.forename: Paul D
authors.initials: PD
authors.lastname: Beer
authors.affiliation: Centre for Advanced ESR (CÆSR), Inorganic Chemistry Laboratory, University of Oxford, South Parks Road, Oxford, OX1 3QR (UK).
authors.forename: Christiane R
authors.initials: CR
authors.lastname: Timmel
authors.affiliation: Chemistry Research Laboratory, University of Oxford, Mansfield Road, Oxford OX1 3TA (UK).
authors.forename: Stephen
authors.initials: S
authors.lastname: Faulkner
keywords: Anionenkoordination; Lanthanoide; Magnetische Anisotropie; NMR‐Spektroskopie; Spektroskopische Methoden