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- Title
Na<sub>4</sub>IrO<sub>4</sub>: Square-Planar Coordination of a Transition Metal in d<sup>5</sup> Configuration due to Weak On-Site Coulomb Interactions.
- Authors
Kanungo, Sudipta; Yan, Binghai; Merz, Patrick; Felser, Claudia; Jansen, Martin
- 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 d8 or d9 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 ground-state 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.
- Subjects
TRANSITION metal compounds; IRIDIUM oxide; COORDINATE covalent bond; COULOMB potential; ELECTRON configuration; SODIUM cobalt oxide; SPIN-orbit interactions; ELECTRONIC structure
- Publication
Angewandte Chemie, 2015, Vol 127, Issue 18, p5507
- ISSN
0044-8249
- Publication type
Article
- DOI
10.1002/ange.201411959