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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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Kanungo,  Sudipta
Max Planck Institute for Chemical Physics of Solids, Max Planck Society;

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Yan,  Binghai
Binghai Yan, Inorganic Chemistry, Max Planck Institute for Chemical Physics of Solids, Max Planck Society;

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Merz,  Patrick
Inorganic Chemistry, Max Planck Institute for Chemical Physics of Solids, Max Planck Society;

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Felser,  Claudia
Claudia Felser, Inorganic Chemistry, Max Planck Institute for Chemical Physics of Solids, Max Planck Society;

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Jansen,  Martin
Inorganic Chemistry, Max Planck Institute for Chemical Physics of Solids, 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. doi:10.1002/anie.201411959.


Cite as: http://hdl.handle.net/11858/00-001M-0000-0026-B52C-1
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.