Electronic structures of bent lanthanide(III) complexes with two N-donor ligands

Hannah M. Nicholas, Michele Vonci, Conrad A.P. Goodwin, Song Wei Loo, Siobhan R. Murphy, Daniel Cassim, Richard E.P. Winpenny, Eric J.L. McInnes, Nicholas F. Chilton, David P. Mills*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

24 Citations (Scopus)

Abstract

Low coordinate metal complexes can exhibit superlative physicochemical properties, but this chemistry is challenging for the lanthanides (Ln) due to their tendency to maximize electrostatic contacts in predominantly ionic bonding regimes. Although a handful of Ln2+ complexes with only two monodentate ligands have been isolated, examples in the most common +3 oxidation state have remained elusive due to the greater electrostatic forces of Ln3+ ions. Here, we report bent Ln3+ complexes with two bis(silyl)amide ligands; in the solid state the Yb3+ analogue exhibits a crystal field similar to its three coordinate precursor rather than that expected for an axial system. This unanticipated finding is in opposition to the predicted electronic structure for two-coordinate systems, indicating that geometries can be more important than the Ln ion identity for dictating the magnetic ground states of low coordinate complexes; this is crucial transferable information for the construction of systems with enhanced magnetic properties.

Original languageEnglish
Pages (from-to)10493-10502
Number of pages10
JournalChemical Science
Volume10
Issue number45
DOIs
Publication statusPublished - 18 Sept 2019
Externally publishedYes

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