Two‐Orbital Three‐Electron Stabilizing Interaction for Direct Co2+As3+ Bonds involving Square‐Planar CoO4 in BaCoAs2O5 |
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Authors: | Rénald David Houria Kabbour Alain Pautrat Nadia Touati Myung‐Hwan Whangbo Olivier Mentré |
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Institution: | 1. Université Lille Nord de France, CNRS UMR8181, Unité de Catalyse et de Chimie du Solide, UCCS USTL, 59655 Villeneuve d'Ascq (France);2. CRISMAT, UMR 6508‐CNRS, ENSICAEN, Caen (France);3. LASIR, UMR 8516, USTL, Villeneuve d'Ascq (France);4. Department of Chemistry, North Carolina State University (USA) |
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Abstract: | The quest for new oxides with cations containing active lone‐pair electrons (E) covers a broad field of targeted specificities owing to asymmetric electronic distribution and their particular band structure. Herein, we show that the novel compound BaCoAs2O5, with lone‐pair As3+ ions, is built from rare square‐planar Co2+O4 involved in direct bonding between As3+E and Co2+ dz2 orbitals (Co? As=2.51 Å). By means of DFT and Hückel calculations, we show that this σ‐type overlapping is stabilized by a two‐orbital three‐electron interaction allowed by the high‐spin character of the Co2+ ions. The negligible experimental spin‐orbit coupling is expected from the resulting molecular orbital scheme in O3AsE–CoO4 clusters. |
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Keywords: | arsenites cobalt electronic structure molecular modeling solid‐state structures |
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