Journal of the American Chemical Society, Vol.140, No.38, 11954-11964, 2018
Unprecedented Bistability in Spin-Crossover Solids Based on the Retroaction of the High Spin Low-Spin Interface with the Crystal Bending
There has been in recent years a continuous increase in spatiotemporal investigations of the dynamics of the first-order transitions in spin-crossover (SCO) solids. In single crystals, this phenomenon proceeds via a single domain nucleation and propagation, characterized in some systems with the presence of two equivalent and symmetric interface orientations, between the high-spin (HS) and low-spin (LS) phases, due to the anisotropic structural change of the unit cell at the transition. The present investigations bring an experimental evidence of the reversible driving of the translational and rotational degrees of freedom of the HS LS interface. In addition to its rectilinear displacement, the interface rotates between two stable angles, 60 and 120. It is demonstrated that while the translation motion is accompanied by a crystal's length change, the interface rotation is controlled by the crystal's bending. These results are well-explained in the frame of an elastic theoretical description in which the effect of the crystal bending, on the stability of the interface's orientation, is simulated by applying a moment of forces on the crystal. It is found that the interface orientation becomes unstable beyond a threshold load value, announcing the emergence of a bistability in SCO solids, taking place at constant HS fraction and volume. This work underlines the sensitive character of the interface orientation to any macroscopic crystal bending, an idea that can be used to develop a new generation of robust stress sensors, working at constant volume, thus avoiding deterioration problems due to crystal fatigue.