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Issue 45, 2019
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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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Supplementary files

Article information


Submitted
11 Jul 2019
Accepted
17 Sep 2019
First published
18 Sep 2019

This article is Open Access
All publication charges for this article have been paid for by the Royal Society of Chemistry

Chem. Sci., 2019,10, 10493-10502
Article type
Edge Article

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, 10, 10493
DOI: 10.1039/C9SC03431E

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