Challenging lanthanide relaxation theory: erbium and thulium complexes that show NMR relaxation rates faster than dysprosium and terbium analogues.
Identifieur interne : 000177 ( Main/Exploration ); précédent : 000176; suivant : 000178Challenging lanthanide relaxation theory: erbium and thulium complexes that show NMR relaxation rates faster than dysprosium and terbium analogues.
Auteurs : Alexander M. Funk [Royaume-Uni] ; Peter Harvey ; Katie-Louise N A. Finney ; Mark A. Fox ; Alan M. Kenwright ; Nicola J. Rogers ; P Kanthi Senanayake ; David ParkerSource :
- Physical chemistry chemical physics : PCCP [ 1463-9084 ] ; 2015.
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.
DOI: 10.1039/c5cp02210j
PubMed: 26051749
Affiliations:
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Kenwright</name></author><author><name sortKey="Rogers, Nicola J" sort="Rogers, Nicola J" uniqKey="Rogers N" first="Nicola J" last="Rogers">Nicola J. Rogers</name></author><author><name sortKey="Senanayake, P Kanthi" sort="Senanayake, P Kanthi" uniqKey="Senanayake P" first="P Kanthi" last="Senanayake">P Kanthi Senanayake</name></author><author><name sortKey="Parker, David" sort="Parker, David" uniqKey="Parker D" first="David" last="Parker">David Parker</name></author></analytic><series><title level="j">Physical chemistry chemical physics : PCCP</title><idno type="eISSN">1463-9084</idno><imprint><date when="2015" type="published">2015</date></imprint></series></biblStruct></sourceDesc></fileDesc><profileDesc><textClass></textClass></profileDesc></teiHeader><front><div type="abstract" xml:lang="en">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.</div></front></TEI><affiliations><list><country><li>Royaume-Uni</li></country></list><tree><noCountry><name sortKey="Finney, Katie Louise N A" sort="Finney, Katie Louise N A" uniqKey="Finney K" first="Katie-Louise N A" last="Finney">Katie-Louise N A. Finney</name><name sortKey="Fox, Mark A" sort="Fox, Mark A" uniqKey="Fox M" first="Mark A" last="Fox">Mark A. Fox</name><name sortKey="Harvey, Peter" sort="Harvey, Peter" uniqKey="Harvey P" first="Peter" last="Harvey">Peter Harvey</name><name sortKey="Kenwright, Alan M" sort="Kenwright, Alan M" uniqKey="Kenwright A" first="Alan M" last="Kenwright">Alan M. Kenwright</name><name sortKey="Parker, David" sort="Parker, David" uniqKey="Parker D" first="David" last="Parker">David Parker</name><name sortKey="Rogers, Nicola J" sort="Rogers, Nicola J" uniqKey="Rogers N" first="Nicola J" last="Rogers">Nicola J. Rogers</name><name sortKey="Senanayake, P Kanthi" sort="Senanayake, P Kanthi" uniqKey="Senanayake P" first="P Kanthi" last="Senanayake">P Kanthi Senanayake</name></noCountry><country name="Royaume-Uni"><noRegion><name sortKey="Funk, Alexander M" sort="Funk, Alexander M" uniqKey="Funk A" first="Alexander M" last="Funk">Alexander M. 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