Solvent-Mediated Chiral Self-Assembly of Nanosized π‑Conjugated Polyhedral Oligomeric Silsesquioxane toward Full Spectrum Luminescence

Developing chiral self-assembly systems with novel properties is of vital importance in expanding the methodology and toolbox in functional chiroptical materials. Manipulating supramolecular chirality and self-assembly behaviors of atomically precise nanosized building blocks remains a great challenge with respect to the molecular design as well as the subsequent rational control through kinetic or thermodynamic protocols. Here, we designed and synthesized a benzoperylene-conjugated polyhedral oligomeric silsesquioxane (POSS) building unit with amino acids as tethers. The nanosized compounds show solvent-polarity-sensitive chiral self-assembly ascribed to the apolar POSS segments. It realized rational control over the emergence of supramolecular chirality as well as helical parameters using water fractions. The self-assembly performed as a chiral matrix to accommodate polyaromatic hydrocarbon guests to enable a multiple-component coassembly through a charge-transfer interaction. Importantly, by virtue of solvent sensitivity and CT-driven coassembly, full-color luminescence including white-light emission was achieved with high quantum yields. This work explored the solvent-sensitive chiral self-assembly and coassemblies of π-conjugated nanosized building units and realized multiple luminescent color conversions, which show potential applications in sensing and chiroptical applications.