Optical imaging of the stochastic nucleation kinetics and intrinsic activation energy of single spin-crossover nanoparticles

Cooperative spin crossover (SCO) compounds are one of the most promising molecular bistable solids due to their intriguing thermal hysteresis phenomena around room temperature. It is well known that hysteresis is an essential kinetic effect, however, accurate assessment of the spin transition kinetics of SCO nanomaterials remains scarce. Herein, we developed a thermal-optical methodology to image the thermally induced spin transition kinetics of single SCO nanoparticles in a quantitative, repeatable, and high-throughput manner. Single-particle measurement revealed an intrinsic nucleation-dominated spin transition mechanism, where a highly stochastic nucleation process was clearly observed during the repeatable measurements. By quantifying the dependence of nucleation time on temperature, the activation energy barriers for nucleation were further extracted at a single particle level. Based on this foundation, the high throughput of the optical imaging not only contributed to uncovering the significant nanoparticle-to-nanoparticle heterogeneity, with implications for a negative correlation between apparent activation energy barriers for nucleation and size of the SCO nanoparticles, but also facilitated identifying a minority with high activation energy at least twice the average value. The extraordinary performance was then attributed to the fewer defects within their structures, as confirmed by further results from the in situ creation of defects by thermal ablation, thereby setting the lower limit for the intrinsic activation energy of ideal SCO crystals and promising their potential for future applications in high-performance molecular devices.