title: Fluoride Binding and Crystal-Field Analysis of Lanthanide Complexes of Tetrapicolyl-Appended Cyclen.
abstract: Lanthanide complexes of tetrapicolyl cyclen displayed remarkably high affinities for fluoride (log K≈5) in water, and were shown to form 1:1 complexes. The behaviour of these systems can be rationalised by changes to the magnitude of the crystal-field parameter, B20 . However, such changes are not invariably accompanied by a change in sign of this parameter: for early lanthanides, the N8 donor set with a coordinated axial water molecule ensures that the magnetic anisotropy has the opposite sense to that observed in the analogous dehydrated lanthanide complexes.
authors.affiliation: Chemistry Research Laboratory, Oxford University, 12 Mansfield Road, Oxford, OX1 3TA, UK.
authors.forename: Octavia A
authors.initials: OA
authors.lastname: Blackburn
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, Oxford University, 12 Mansfield Road, Oxford, OX1 3TA, UK.
authors.forename: Andrew R
authors.initials: AR
authors.lastname: Jupp
authors.affiliation: Chemistry Research Laboratory, Oxford University, 12 Mansfield Road, Oxford, OX1 3TA, UK.
authors.forename: Jose M
authors.initials: JM
authors.lastname: Goicoechea
authors.affiliation: Chemistry Research Laboratory, Oxford University, 12 Mansfield Road, Oxford, OX1 3TA, UK.
authors.forename: Paul D
authors.initials: PD
authors.lastname: Beer
authors.affiliation: Chemistry Research Laboratory, Oxford University, 12 Mansfield Road, Oxford, OX1 3TA, UK. stephen.faulkner@keble.ox.ac.uk.
authors.forename: Stephen
authors.identifier: http://orcid.org/0000-0003-1878-5857
authors.initials: S
authors.lastname: Faulkner
keywords: NMR spectroscopy; crystal field; fluorides; lanthanides; magnetic anisotropy