Molecular Aggregation Dynamics via a Liquid-like Cluster Intermediate during Heterogeneous Evaporation as Revealed by...

A hyperspectral camera (HSC) is a camera with great potential to obtain spectral information at each pixel, together with spatial imaging. HSC fluorescence imaging enables the molecular aggregation dynamics of the evaporative crystallization process to be followed in real-time. The key intermediate liquid-like cluster state for the two-step nucleation mechanism is visualized by the fluorescence color changes of mechanochromic luminescent dibenzoylmethanatoboron difluoride derivatives. Three types of emissive species (Crystal, BG-aggregates, and Amorphous) are generated from monomers in solution (low order and density) via liquid-like cluster (high density and low order) during solvent evaporation. These emissive species have partially different aggregated states based on fluorescence decay and fluorescence excitation spectral measurements. In terms of crystallization dynamics, our results indicate that it is important not only to generate supersaturated states but also to maintain the survival time of the liquid-like cluster. Moreover, we demonstrate that HSC fluorescence imaging can be a powerful tool for visualizing heterogeneous molecular aggregation processes.