Axial fluoride binding by lanthanide DTMA complexes alters the local crystal field, resulting in dramatic spectroscopic changes

Abstract

Addition of fluoride to aqueous solutions of lanthanide complexes of DTMA results in the formation of ternary complexes of the form [F·Ln·DTMA]²⁺ in which an axial solvent molecule is displaced by fluoride. [F·Ln·DTMA]²⁺ and [H₂O·Ln·DTMA]³⁺ are in exchange on a timescale of around 1 s. Dramatic changes are observed in both the NMR and luminescence spectra of the complexes: these are consistent with a change in the nature of the magnetic anisotropy at the paramagnetic lanthanide centre, itself arising from a change in the local crystal field. Study of paramagnetic lanthanide complexes with anisotropic electronic distributions reveals that, upon replacing water with fluoride, there is an inversion of the sign, and a significant reduction in the magnitude, of the crystal field term that defines the nature of the pseudocontact shift.