Liquid–Liquid Phase Separation Mediated Formation of Chiral 2D Crystalline Nanosheets of a Co‐Assembled System

Abstract The role of macromolecule‐macromolecule and macromolecule–H₂O interactions and the resulting perturbation of the H‐bonded network of H₂O in the liquid–liquid phase separation (LLPS) process of biopolymers are well‐known. However, the potential of the hydrated state of supramolecular structures (non‐covalent analogs of macromolecules) of synthetic molecules is not widely recognized for playing a similar role in the LLPS process. Herein, LLPS occurred during the co‐assembly of hydrated supramolecular vesicles (bolaamphiphile, BA1) with a net positive charge (zeta potential, ζ = +60 ± 2 mV) and a dianionic chiral molecule (disodium l‐[+]‐tartrate) is reported. As inferred from cryo‐transmission electron microscopy (TEM), the LLPS‐formed droplets serve as the nucleation precursors, dictating the structure and properties of the co‐assembly. The co‐assembled structure formed by LLPS effectively integrates the counter anion's asymmetry, resulting in the formation of ultrathin free‐standing, chiral 2D crystalline sheets. The significance of the hydrated state of supramolecular structures in influencing LLPS is unraveled through studies extended to a less hydrated supramolecular structure of a comparable system (BA2). The role of LLPS in modulating the hydrophobic interaction in water paves the way for the creation of advanced functional materials in an aqueous environment.