Supramolecular Nanostructures of Chiral Perylene Diimides with Amplified Chirality for High-Performance Chiroptical Sensing

Chiral supramolecular nanostructures with optoelectronic functions are expected to play a central role in many scientific and technological fields but their practical use remains in its infancy. Here, this paper reports photoconductive chiral organic semiconductors (OSCs) based on perylene diimides with the highest electron mobility among the chiral OSCs and investigates the structure and optoelectronic properties of their homochiral and heterochiral supramolecular assemblies from bottom-up self-assembly. Owing to the well-ordered supramolecular packing, the homochiral nanomaterials exhibit superior charge transport with significantly higher photoresponsivity and dissymmetry factor compared with those of their thin film and monomeric equivalents, which enables highly selective detection of circularly polarized light, for the first time, in visible spectral range. Interestingly, the heterochiral nanostructures assembled from co-self-assembly of racemic mixtures show extraordinary chiral self-discrimination phenomenon, where opposite enantiomeric molecules are packed alternately into heterochiral architectures, leading to completely different optoelectrical performances. In addition, the crystal structures of homochiral and heterochiral nanostructures have first been studied by ab initio X-ray powder diffraction analysis. These findings give insights into the structure-chiroptical property relationships of chiral supramolecular self-assemblies and demonstrate the feasibility of supramolecular chirality for high-performance chiroptical sensing.