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Beyond Bleaney's Theory: Experimental and Theoretical Analysis of Periodic Trends in Lanthanide‐Induced Chemical Shift
Author(s) -
Suturina Elizaveta A.,
Mason Kevin,
Geraldes Carlos F. G. C.,
Kuprov Ilya,
Parker David
Publication year - 2017
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201706931
Subject(s) - isostructural , lanthanide , paramagnetism , ab initio , materials science , ab initio quantum chemistry methods , ligand (biochemistry) , crystallography , chemistry , molecule , condensed matter physics , crystal structure , physics , ion , biochemistry , receptor , organic chemistry
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.