Domain Wall Dynamics in a Ferroelastic Spin Crossover Complex with Giant Magnetoelectric Coupling.

Pinned and mobile ferroelastic domain walls are detected in response to mechanical stress in a Mn 3+ complex with two-step thermal switching between the spin triplet and spin quintet forms. Single-crystal X-ray diffraction and resonant ultrasound spectroscopy on [Mn III (3,5-diCl-sal 2 (323))]BPh 4 reveal three distinct symmetry-breaking phase transitions in the polar space group series Cc → Pc → P 1 → P 1 (1/2) . The transition mechanisms involve coupling between structural and spin state order parameters, and the three transitions are Landau tricritical, first order, and first order, respectively. The two first-order phase transitions also show changes in magnetic properties and spin state ordering in the Jahn-Teller-active Mn 3+ complex. On the basis of the change in symmetry from that of the parent structure, Cc , the triclinic phases are also ferroelastic, which has been confirmed by resonant ultrasound spectroscopy. Measurements of magnetoelectric coupling revealed significant changes in electric polarization at both the Pc → P 1 and P 1 → P 1 (1/2) transitions, with opposite signs. All these phases are polar, while P 1 is also chiral. Remanent electric polarization was detected when applying a pulsed magnetic field of 60 T in the P 1→ P 1 (1/2) region of bistability at 90 K. Thus, we showcase here a rare example of multifunctionality in a spin crossover material where the strain and polarization tensors and structural and spin state order parameters are strongly coupled.