Sequential Activation of Molecular and Macroscopic Spin-State Switching within the Hysteretic Region Following Pulsed...

Molecular spin-crossover (SCO) compounds constitute a promising class of photoactive materials exhibiting efficient photoinduced phase transitions (PIPTs). Taking advantage of the unique, picture-perfect reproducibility of the spin-transition properties in the compound [Fe(HB(1,2,4-triazol-1-yl)₃ )₂ ], the spatiotemporal dynamics of the PIPT within the thermodynamic metastability (hysteretic) region of a single crystal is dissected, using pump-probe optical microscopy. Beyond a threshold laser-excitation density, complete PIPTs are evidenced, with conversion rates up to 200 switched molecules per absorbed photon. It is shown that the PIPT takes place through the sequential activation of two (molecular and macroscopic) switching mechanisms, occurring on sub-microsecond and millisecond timescales, governed by the intramolecular and free energy barriers of the system, respectively. The main finding here is that the thermodynamic metastability has strictly no influence on the sub-millisecond switching dynamics. Indeed, before this millisecond timescale, the response of the crystal to the laser excitation involves a gradual, molecular conversion process, as if there were no hysteresis loop. Consequently, in this regime, even a 100% photoinduced conversion may not give rise to a PIPT. These results provide new insight on the intrinsic dynamical limits of the PIPT, which is an important issue from a technological perspective.