Near-room-temperature magnetoelectric coupling engineered through inversion-breaking tilts in a bulk perovskite polytype

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Systematic strategies to design properties such as ferroelectricity or magnetoelectric coupling are well established in simple perovskite materials, but they remain scarce in more complex framework structures. Using a hexagonal polytype of the ternary manganite AMnO3 (A = Ba, Sr, Ca) as a model system, we introduce a symmetry-guided design principle in which an inversion-breaking rigid-unit mode (RUM) serves as a single structural instability generating both polar and ferromagnetic orders within a bulk material. Symmetry analysis and first-principles calculations reveal that co-operative tilts of the Mn2O9 bioctahedral dimers generate both a spontaneous polarization and a ferromagnetic moment. High-resolution diffraction and magnetic susceptibility measurements show the structural and magnetic orders persist as high as 450 K and 280 K, respectively, highlighting the untapped potential of framework structures which deviate from simple perovskite motifs to be designed to host useful ferroic properties. Our approach establishes a transferable symmetry-based framework to engineer ferroelectric and magnetoelectric states across chemically diverse framework architectures.