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A-site ordered perovskite CaCu3Cu2Ir2O12−δ with square-planar and octahedral coordinated Cu ions

A novel CaCu3Cu2Ir2O12−δ polycrystalline sample was synthesized at 8 GPa and 1373 K. Rietveld structural analysis shows that this compound crystallizes in an -type A-site ordered perovskite structure with space group Im-3. X-ray absorption spectra reveal a +2-charge state for both the square-planar and octahedral coordinated Cu ions, and the valence state of Ir is found to be about +5. Although the A-site Ca and the A′-site Cu2+ are 1:3 ordered at fixed atomic positions, the distribution of B-site Cu2+ and Ir5+ is disorderly. As a result, no long-range magnetic ordering is observed at temperatures down to 2 K. Electrical transport and heat capacity measurements demonstrate itinerant electronic behavior. The crystal structure is stable with pressure up to 35.7 GPa at room temperature.