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

Elizaveta A. Suturina, Kevin Mason, Carlos F.G.C. Geraldes, Ilya Kuprov, David Parker

Research output: Contribution to journalArticlepeer-review

29 Citations (Scopus)

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.

Original languageEnglish
Pages (from-to)12215-12218
Number of pages4
JournalAngewandte Chemie - International Edition
Volume56
Issue number40
Early online date24 Aug 2017
DOIs
Publication statusPublished - 20 Sep 2017

Keywords

  • lanthanides
  • ligand field
  • paramagnetic NMR
  • PARASHIFT
  • pseudocontact shift

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)

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