Tuning the Geometry and Optical Chirality of Pentatwinned Au Nanoparticles with 5-Fold Rotational Symmetry.

Chirality transfer from chiral molecules to chiral nanomaterials represents an important topic for exploring the origin of chirality in many natural and artificial systems. Moreover, developing a promising class of chiral nanomaterials holds great significance for various applications, including sensing, photonics, catalysis, and biomedicine. Here we demonstrate the geometric control and tunable optical chirality of chiral pentatwinned Au nanoparticles with 5-fold rotational symmetry using the seed-mediated chiral growth method. A distinctive growth pathway and optical chirality are observed using pentatwinned decahedra as seeds, in comparison with the single-crystal Au seeds. By employing different peptides as chiral inducers, pentatwinned Au nanoparticles with two distinct geometric chirality (pentagonal nanostars and pentagonal prisms) are obtained. The intriguing formation and evolution of geometric chirality with the twinned structure are analyzed from a crystallographic perspective upon maneuvering the interplay of chiral molecules, surfactants, and reducing agents. Moreover, the interesting effects of the molecular structure of peptides on tuning the geometric chirality of pentatwinned Au nanoparticles are also explored. Finally, we theoretically and experimentally investigate the far-field and near-field optical properties of chiral pentatwinned Au nanoparticles through numerical simulations and single-particle chiroptical measurements. The ability to tune the geometric chirality in a controlled manner represents an important step toward the development of chiral nanomaterials with increasing architectural complexity for chiroptical applications.