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Challenging lanthanide relaxation theory : erbium and thulium complexes that show NMR relaxation rates faster than dysprosium and terbium analogues.

Funk, A.M. and Harvey, P. and Finney, K.-L.N.A. and Fox, M.A. and Kenwright, A.M. and Rogers, N.J. and Senanayake, P.K. and Parker, D. (2015) 'Challenging lanthanide relaxation theory : erbium and thulium complexes that show NMR relaxation rates faster than dysprosium and terbium analogues.', Physical chemistry chemical physics., 17 (25). pp. 16507-16511.

Abstract

Measurements of the proton NMR paramagnetic relaxation rates for several series of isostructural lanthanide(III) complexes have been performed in aqueous solution over the field range 1.0 to 16.5 Tesla. The field dependence has been modeled using Bloch–Redfield–Wangsness theory, allowing values for the electronic relaxation time, Tle and the magnetic susceptibility, μeff, to be estimated. Anomalous relaxation rate profiles were obtained, notably for erbium and thulium complexes of low symmetry 8-coordinate aza-phosphinate complexes. Such behaviour challenges accepted theory and can be interpreted in terms of changes in Tle values that are a function of the transient ligand field induced by solvent collision and vary considerably between Ln3+ ions, along with magnetic susceptibilities that deviate significantly from free-ion values.

Item Type:Article
Full text:(AM) Accepted Manuscript
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Status:Peer-reviewed
Publisher Web site:http://dx.doi.org/10.1039/C5CP02210J
Date accepted:02 June 2015
Date deposited:28 July 2015
Date of first online publication:02 June 2015
Date first made open access:02 June 2016

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