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Issue 45, 2015
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Axial fluoride binding by lanthanide DTMA complexes alters the local crystal field, resulting in dramatic spectroscopic changes

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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.

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

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Publication details

The article was received on 24 Jun 2015, accepted on 16 Jul 2015 and first published on 17 Jul 2015


Article type: Paper
DOI: 10.1039/C5DT02398J
Citation: Dalton Trans., 2015,44, 19509-19517
  • Open access: Creative Commons BY license
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    Axial fluoride binding by lanthanide DTMA complexes alters the local crystal field, resulting in dramatic spectroscopic changes

    O. A. Blackburn, A. M. Kenwright, P. D. Beer and S. Faulkner, Dalton Trans., 2015, 44, 19509
    DOI: 10.1039/C5DT02398J

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