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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 (CoAs=2.51...
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