Regulating of Liquid-Liquid Phase Separation and Molecular Self-Assembly through Selective Solvation

Effectively regulating the liquid-liquid phase separation (LLPS) phenomenon in the process of molecular self-assembly is critical for controlling the qualities of the final products. However, the underlying mechanisms of LLPS that greatly affect the transition from molecules to crystals have not been fully addressed. Here, target solvents with properties of solvation or selective solvation suppression were theoretically screened to regulate the emergence and elimination of LLPS. Quantitative analysis of molecular electrostatic potential surfaces (MESP) was first applied to screen the antisolvent with solvation suppressing effect. Selective solvation suppressing was revealed, and the evolution mechanism of self-assembly in the nucleation pathways with or without LLPS was explored by experiments. It was found that clusters with unique properties of core-shell structure with dispersion transition layer may be the key to the occurrence of LLPS. This further provides new insights for understanding LLPS, which is a typical case for nonclassical nucleation theory.