Issue 45, 2019

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

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

Supplementary files

Article information

Article type
Edge Article
Submitted
11 juil. 2019
Accepted
17 sept. 2019
First published
18 sept. 2019
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY license

Chem. Sci., 2019,10, 10493-10502

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

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

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