Domain wall motion is detected for the first time during the transition to a ferroelastic and spin state ordered phase of a spin crossover complex. Single‐crystal X‐ray diffraction and resonant ultrasound spectroscopy (RUS) revealed two distinct symmetry‐breaking phase transitions in the mononuclear Mn 3+ compound [Mn(3,5‐diBr‐sal 2 (323))]BPh 4 , 1. The first at 250 K, involves the space group change Cc → Pc and is thermodynamically continuous, while the second, Pc → P 1 at 85 K, is discontinuous and related to spin crossover and spin state ordering. Stress‐induced domain wall mobility was interpreted on the basis of a steep increase in acoustic loss immediately below the the Pc ‐ P 1 transition

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.

Domain wall motion is detected for the first time during the transition to af erroelastic and spin state ordered phase of as pin crossover complex. Single-crystal X-ray diffraction and resonant ultrasound spectroscopy(RUS) revealed two distinct symmetry-breaking phase transitions in the mononuclear Mn 3+ compound [Mn(3,5-diBr-sal 2-(323))]BPh 4 ,1 .T he first at 250 K, involves the space group change Cc!Pc and is thermodynamically continuous,w hile the second, Pc!P1 at 85 K, is discontinuous and related to spin crossover and spin state ordering. Stress-induced domain wall mobility was interpreted on the basis of asteep increase in acoustic loss immediately belowt he the Pc-P1 transition

Structural, magnetic and spectroscopic data on four new spin triplet Mn3+ complexes reveals a large magnetic anisotropy. Spin state is sensitive to lattice contents as the spin quintet ground state is stabilized on co-crystallization with ethanol.

A MnIII spin crossover complex with atypical two‐step hysteretic thermal switching at 74 K and 84 K shows rich structural–magnetic interplay and magnetic‐field‐induced spin state switching below 14 T with an onset below 5 T. The spin states, structures, and the nature of the phase transitions are elucidated via X‐ray and magnetization measurements. An unusual intermediate phase containing four individual sites, where 1/4 are in a pure low spin state, is observed. The splitting of equivalent sites in the high temperature phase into four inequivalent sites is due to a structural reorganization involving a primary and a secondary symmetry‐breaking order parameter that induces a crystal system change from orthorhombic→monoclinic and a cell doubling. Further cooling leads to a reconstructive phase transition and a monoclinic low‐temperature phase with two inequivalent low‐spin sites. The coupling between the order parameters is identified in the framework of Landau theory.