Re-Appearance of Cooperativity in Ultra-Small Spin-Crossover [Fe(pz){Ni(CN) 4 }] Nanoparticles

Abstract : A reverse nanoemulsion technique was used for the elaboration of [Fe(pz){Ni(CN)4}] nanoparticles. Low‐temperature micellar exchange made it possible to elaborate ultra‐small nanoparticles with sizes down to 2 nm. When decreasing the size of the particles from 110 to 12 nm the spin transition shifts to lower temperatures, becomes gradual, and the hysteresis shrinks. On the other hand, a re‐opening of the hysteresis was observed for smaller (2 nm) particles. A detailed 57Fe Mössbauer spectroscopy analysis was used to correlate this unusual phenomenon to the modification of the stiffness of the nanoparticles thanks to the determination of their Debye temperature.