Hierarchical Self-Assembly, Nanoarchitectonics, and Emerging Functionalities of Chiral π-Amphiphiles

Rational design of functional building blocks and precise control over their hierarchical self-assembly form the cornerstones of supramolecular chemistry and materials science. Amphiphilic molecules, with their inherent hydrophilic–hydrophobic duality, serve as critical building blocks across several disciplines. Integrating additional functionalities such as π-conjugation and chirality significantly expands the design space and utility of common amphiphiles, giving rise to a new class of building blocks: chiral π-amphiphiles. Typically, a synthetic chiral π-amphiphile consists of two functionally distinct segments, i.e., a hydrophobic π-extended chromophore and a hydrophilic chiral unit, covalently linked via common chemical linkers. The integration of chirality, functional π-systems, and amphiphilicity offers distinct advantages, such as chirality-guided directional π-stacking and superior chiroptical properties arising from their hierarchical chiral architectures in both organic and aqueous phases. Emerging chiral functions of chiral π-amphiphiles including circularly polarized luminescence, chiral recognition and separation, chiral biomedicine, and spin electronics have witnessed groundbreaking progress in recent years, which we believe will contribute to the development of novel chiral materials through molecular self-assembly approaches. This review systematically summarizes and discusses the definition, molecular design strategies, classification, nanostructures, applications, and future perspectives of chiral π-amphiphiles, aiming to help scientists evaluate the cutting-edge field of chirality science via diverse supramolecular technologies and systematic molecular engineering.