Beyond Bleaney's Theory: Experimental and Theoretical Analysis of Periodic Trends in Lanthanide Induced Chemical Shift

Parker, David; Kuprov, Ilya; Suturina, Elizaveta; Mason, Kevin; Geraldes, Carlos

doi:10.1002/anie.201706931

Beyond Bleaney's Theory: Experimental and Theoretical Analysis of Periodic Trends in Lanthanide Induced Chemical Shift

Parker, David; Kuprov, Ilya; Suturina, Elizaveta; Mason, Kevin; Geraldes, Carlos

Authors

Professor David Parker david.parker@durham.ac.uk
Emeritus Professor

Ilya Kuprov

Elizaveta Suturina

Kevin Mason

Carlos Geraldes

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 as-sumption 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: thus, one of the most popular assumptions about isostructural lanthanide series is incorrect.

Citation

Parker, D., Kuprov, I., Suturina, E., Mason, K., & Geraldes, C. (2017). Beyond Bleaney's Theory: Experimental and Theoretical Analysis of Periodic Trends in Lanthanide Induced Chemical Shift. Angewandte Chemie International Edition, 56(40), 12215-12218. https://doi.org/10.1002/anie.201706931

Journal Article Type	Article
Acceptance Date	Aug 1, 2017
Online Publication Date	Aug 24, 2017
Publication Date	Sep 25, 2017
Deposit Date	Aug 1, 2017
Publicly Available Date	Aug 24, 2018
Journal	Angewandte Chemie International Edition
Print ISSN	1433-7851
Electronic ISSN	1521-3773
Publisher	Wiley
Peer Reviewed	Peer Reviewed
Volume	56
Issue	40
Pages	12215-12218
DOI	https://doi.org/10.1002/anie.201706931

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Copyright Statement
This is the peer reviewed version of the following article: Parker, David, Kuprov, Ilya, Suturina, Elizaveta, Mason, Kevin & Geraldes, Carlos (2017). Beyond Bleaney's Theory: Experimental and Theoretical Analysis of Periodic Trends in Lanthanide Induced Chemical Shift. Angewandte Chemie International Edition 56(40): 12215-12218, which has been published in final form at https://doi.org/10.1002/anie.201706931. This article may be used for non-commercial purposes in accordance With Wiley-VCH Terms and Conditions for self-archiving.