A family of ionic supersalts with covalent-like directionality and unconventional multiferroicity.

Ionic crystals composed of elemental ions such as NaCl are non-polar due to directionless ionic bonding interactions. Here, we show that these can develop polarity by changing their building blocks from elemental ions to superalkali and superhalogen cluster-ions, which mimic the chemistry of alkali and halogen atoms, respectively. Due to the non-spherical geometries of these cluster ions, corresponding supersalts form anisotropic polar structures with ionic bonding, yet covalent-like directionality, akin to sp³ hybridized systems. Using density functional theory and extensive structure searches, we predict a series of stable ferroelectric/ferroelastic supersalts, PnH₄MX₄ (Pn = N, P; M = B, Al, Fe; X = Cl, Br) composed of superalkali PnH₄ and superhalogen MX₄ ions. Unlike traditional ferroelectric/ferroelastic materials, the cluster-ion based supersalts possess ultra-low switching barrier and can endure large ion displacements and reversible strain. In particular, PH₄FeBr₄ exhibits triferroic coupling of ferroelectricity, ferroelasticity, and antiferromagnetism with controllable spin directions via either ferroelastic or 90-degree ferroelectric switching.