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

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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.

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

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Publication details

The article was received on 11 Jul 2019, accepted on 17 Sep 2019 and first published on 18 Sep 2019


Article type: Edge Article
DOI: 10.1039/C9SC03431E
Chem. Sci., 2019, Advance Article
  • Open access: Creative Commons BY license
    All publication charges for this article have been paid for by the Royal Society of Chemistry

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

    H. M. Nicholas, M. Vonci, C. A. P. Goodwin, S. W. Loo, S. R. Murphy, D. Cassim, R. E. P. Winpenny, E. J. L. McInnes, N. F. Chilton and D. P. Mills, Chem. Sci., 2019, Advance Article , DOI: 10.1039/C9SC03431E

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