Publication details for Prof. David ParkerParker, 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.
- Publication type: Journal Article
- ISSN/ISBN: 1433-7851 (print), 1521-3773 (electronic)
- DOI: 10.1002/anie.201706931
- Further publication details on publisher web site
- Durham Research Online (DRO) - may include full text
Author(s) from Durham
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.