Beyond Bleaney's theory: experimental and theoretical analysis of periodic trends in lanthanide induced chemical shift
Beyond Bleaney's theory: experimental and theoretical analysis of periodic trends in lanthanide induced chemical shift
A detailed analysis of paramagnetic NMR shifts in a series of isostructural lanthanide complexes relavant to PARASHIFT contrast agents reveals unexpected trends in the magnetic susceptibility anisotropy that cannot be explained by the commonly used Bleaney's theory. Ab initio calculations reveal that the primary assumption of Bleaney's theory – that thermal energy is larger than the ligand field splitting – does not hold for the lanthanide complexes in question, and likely for a large fraction of lanthanide complexes in general. This makes the orientation of the magnetic susceptibility tensor differ significantly between complexes of different lanthanides with the same ligand: one of the most popular assumptions about isostructural lanthanide series is wrong.
12215-12218
Suturina, Elizaveta
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Mason, Kevin
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Geraldes, Carlos F.G.C.
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Kuprov, Ilya
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Parker, David
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Suturina, Elizaveta
24dd007d-949a-4852-99d1-ea42b00103ef
Mason, Kevin
b44d68df-9067-4812-a742-ff17df162f4b
Geraldes, Carlos F.G.C.
c109bc54-a4f6-4d80-8bc8-bf30f8d3fce1
Kuprov, Ilya
bb07f28a-5038-4524-8146-e3fc8344c065
Parker, David
31bfb567-907a-4490-af57-411089ae0e73
Suturina, Elizaveta, Mason, Kevin, Geraldes, Carlos F.G.C., Kuprov, Ilya and Parker, David
(2017)
Beyond Bleaney's theory: experimental and theoretical analysis of periodic trends in lanthanide induced chemical shift.
Angewandte Chemie International Edition, 56 (40), .
(doi:10.1002/anie.201706931).
Abstract
A detailed analysis of paramagnetic NMR shifts in a series of isostructural lanthanide complexes relavant to PARASHIFT contrast agents reveals unexpected trends in the magnetic susceptibility anisotropy that cannot be explained by the commonly used Bleaney's theory. Ab initio calculations reveal that the primary assumption of Bleaney's theory – that thermal energy is larger than the ligand field splitting – does not hold for the lanthanide complexes in question, and likely for a large fraction of lanthanide complexes in general. This makes the orientation of the magnetic susceptibility tensor differ significantly between complexes of different lanthanides with the same ligand: one of the most popular assumptions about isostructural lanthanide series is wrong.
Text
Parker_et_al-2017-Angewandte_Chemie_International_Edition
- Accepted Manuscript
More information
Accepted/In Press date: 1 August 2017
e-pub ahead of print date: 24 August 2017
Identifiers
Local EPrints ID: 414917
URI: http://eprints.soton.ac.uk/id/eprint/414917
ISSN: 1433-7851
PURE UUID: 05e3b5da-185b-467c-90e8-c9917a176e39
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Date deposited: 16 Oct 2017 16:31
Last modified: 16 Mar 2024 05:37
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Contributors
Author:
Elizaveta Suturina
Author:
Kevin Mason
Author:
Carlos F.G.C. Geraldes
Author:
David Parker
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