Na4IrO4: Square-Planar Coordination of a Transition Metal in d5 Configuration 
due to Weak On-Site Coulomb Interactions

Kanungo, S.; Yan, B.; Merz, P.; Felser, C.; Jansen, M.

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Na₄IrO₄: Square-Planar Coordination of a Transition Metal in d⁵ Configuration due to Weak On-Site Coulomb Interactions

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Jansen, M.
Abteilung Jansen, Former Departments, Max Planck Institute for Solid State Research, Max Planck Society;

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Citation

Kanungo, S., Yan, B., Merz, P., Felser, C., & Jansen, M. (2015). Na₄IrO₄: Square-Planar Coordination of a Transition Metal in d⁵ Configuration due to Weak On-Site Coulomb Interactions. Angewandte Chemie International Edition, 54(18), 5417-5420.

Cite as: https://hdl.handle.net/21.11116/0000-000E-CB14-7

Abstract

Local environments and valence electron counts primarily determine the electronic states and physical properties of transition-metal complexes. For example, square-planar coordination geometries found in transition-metal oxometalates such as cuprates are usually associated with the d(8) or d(9) electron configuration. In this work, we address an unusual square-planar single oxoanionic [IrO4](4-) species, as observed in Na4IrO4 in which IrIV has a d5 configuration, and characterize the chemical bonding through experiments and by ab initio calculations. We find that the IrIV center in groundstate Na4IrO4 has square-planar coordination geometry because of the weak Coulomb repulsion of the Ir-5d electrons. In contrast, in its 3d counterpart Na4CoO4, the CoIV center is tetrahedrally coordinated because of strong electron correlation. Na4IrO4 may thus serve as a simple yet important example to study the ramifications of Hubbard-type Coulomb interactions on local geometries.