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Funk AM, Harvey P, Finney KL, et al. Challenging lanthanide relaxation theory: erbium and thulium complexes that show NMR relaxation rates faster than dysprosium and terbium analogues. Phys Chem Chem Phys. 2015;17(25):16507-11doi: 10.1039/c5cp02210j.
Funk, A. M., Harvey, P., Finney, K. L., Fox, M. A., Kenwright, A. M., Rogers, N. J., Senanayake, P. K., & 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 : PCCP, 17(25), 16507-11. https://doi.org/10.1039/c5cp02210j
Funk, Alexander M, et al. "Challenging lanthanide relaxation theory: erbium and thulium complexes that show NMR relaxation rates faster than dysprosium and terbium analogues." Physical chemistry chemical physics : PCCP vol. 17,25 (2015): 16507-11. doi: https://doi.org/10.1039/c5cp02210j
Funk AM, Harvey P, Finney KL, Fox MA, Kenwright AM, Rogers NJ, Senanayake PK, Parker D. Challenging lanthanide relaxation theory: erbium and thulium complexes that show NMR relaxation rates faster than dysprosium and terbium analogues. Phys Chem Chem Phys. 2015 Jul 07;17(25):16507-11. doi: 10.1039/c5cp02210j. Epub 2015 Jun 08. PMID: 26051749.
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Phys Chem Chem Phys. 2015 Jul 07;17(25):16507-11. doi: 10.1039/c5cp02210j. Epub 2015 Jun 08.

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

Physical chemistry chemical physics : PCCP

Alexander M Funk, Peter Harvey, Katie-Louise N A Finney, Mark A Fox, Alan M Kenwright, Nicola J Rogers, P Kanthi Senanayake, David Parker

Affiliations

  1. Department of Chemistry, Durham University, South Road, Durham DH1 3LE, UK. [email protected].

PMID: 26051749 DOI: 10.1039/c5cp02210j

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 Ln(3+) ions, along with magnetic susceptibilities that deviate significantly from free-ion values.

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