Chiral Ligand-Free, Optically Active Nanoparticles Inherently Composed of Chiral Lattices at the Atomic Scale.

Bulk metals lack chirality. Recently, metals have been sculptured with metastable chirality varying from the micro- to nano-scale. The manipulation of molecular chirality could be novelly performed using metals composed of chiral lattices at atomic scales (i.e., chiral nanoparticles or CNPs) if one could fundamentally understand the interactions between molecules and the chiral metal lattices. The incorporation of chiral ligands has been generally adapted to form metal CNPs. However, post-fabrication removal of chiral ligands usually causes relaxation of the metastable chiral lattices to thermodynamically stable achiral structures, and thus the coexisting chiral ligands will unavoidably disturb or screen the interactions of interest. Herein, a concept of metal CNPs that are free of chiral ligands and consist of atomically chiral lattices is introduced. Without chiral ligands, shear forces applied by substrate rotation along with the translation of incident atoms lead to imposing the metastable chiral lattices onto metals. Metal CNPs show not only the chiroptical effect but the enantiospecific interactions of chiral lattices and molecules. These two unique chiral effects have resulted in the applications of enantiodifferentiation and asymmetric synthesis. Prospectively, the extension in composition space and constituent engineering will apply alloy CNPs to enantiodiscrimination, enantioseperation, bio-imaging, bio-sensing, and asymmetric catalysis.