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Beyond Bleaney's theory : experimental and theoretical analysis of periodic trends in lanthanide induced chemical shift.

Parker, David and Kuprov, Ilya and Suturina, Elizaveta and Mason, Kevin and 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). pp. 12215-12218.


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.

Item Type:Article
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Publisher 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 This article may be used for non-commercial purposes in accordance With Wiley-VCH Terms and Conditions for self-archiving.
Date accepted:01 August 2017
Date deposited:02 August 2017
Date of first online publication:24 August 2017
Date first made open access:24 August 2018

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