Tertiary Chiral Nanostructures from C-H⋅⋅⋅F Directed Assembly of Chiroptical Superatoms

We report the synthesis and structure of tertiary chiral nanostructures with 100 % optical purity. A novel synthetic strategy, using chiral reducing agent, R and S-BINAPCuBH₄ (BINAP is 2,2'-Bis(diphenylphosphino)-1,1'-binaphthyl), is developed to access to atomically precise, intrinsically chiral [Au₇ Ag₆ Cu₂ (R- or S-BINAP)₃ (SCH₂ Ph)₆ ]SbF₆ nanoclusters in one-pot synthesis. The clusters represent the first tri-metallic superatoms with inherent chirality and fair stability. Both metal distribution (primary) and ligand arrangement (secondary) of the enantiomers exhibited perfect mirror images, and unprecedentedly, the self-assembly driven by the C-H⋅⋅⋅F interaction between the phenyl groups of the superatom moieties and SbF₆ ^- anions induced the formation of bio-mimic left- and right-handed helices, achieving the tertiary chiral nanostructures. DFT calculations revealed the connections between the molecular details and chiral optical activity.