Centrosymmetry Breaking and Ferroelectricity Driven by Short-Range Magnetic Order in the Quadruple Perovskite (YMn 3 )Mn 4 O 12 .

By means of single-crystal X-ray diffraction, we give direct crystallographic evidence of a centrosymmetry breaking below T _S = 200 K, concomitant with the onset of a commensurate structural modulation in the quadruple perovskite YMn ₃ Mn ₄ O ₁₂ . This result, which explains the anomalously large thermal coefficient of the Y ³⁺ ion in previously reported structural models, is attributed to the small size of the Y ³⁺ ion, which causes its underbonding within the dodecahedral coordination polyhedron. The present data are consistent with a commensurate superstructure described by an I-centered pseudo-orthorhombic cell with polar Ia symmetry and a ≈ a _F √2 = 10.4352(7) Å, b ≈ 2 b _F = 14.6049(9) Å, c ≈ c _F √2 = 10.6961(7) Å, and β = 90.110(3)°, where a _F ≈ c _F ≈ 7.45 Å, b _F ≈ 7.34 Å, and β ≈ 91° are the unit cell parameters of the I 2/ m structure observed at room temperature. Consistent with the above polar structure, at lower temperature, T * = 70 K, we observe in polycrystalline samples an anomaly of the direct current (DC) and alternating current (AC) magnetization, concomitant with the appearance of a net electric polarization, as indicated by pyrocurrent and dielectric constant measurements. These results, complemented by electrical transport measurements, suggest a magnetic ferroelectricity driven by short-range magnetic order in YMn ₃ Mn ₄ O ₁₂ .