Self-Regulated Pathway-Dependent Chirality Control of Silver Nanoclusters

Imparting chirality affords additive values, functions and responsiveness in molecular systems including nanoscale materials. Here, we report pathway-dependent chirality control in silver nanoclusters (NCs). The use of enantiomeric ligand, alpha-dihydrolipoic acid (DHLA), for the synthesis of Ag NCs leads to the preferential formation of one-handed chiral Ag-29(DHLA)(12) NCs with intrinsic chirality in the exterior shell composed of a silver-dithiolate framework. Small Lewis base molecules such as pyridine bind to silver atoms in the shell of NC as a guest. The guest binding reverses the relative stability between the right- and left-handed NCs upon a steric interaction with the chiral ligand DHLA in the exterior shell in a kinetic manner, leading to unprecedented chirality inversion in the synthesis of NCs. This mechanism is further extended to the self-regulation or self-replication of chirality through interNC interactions dependent on the concentration in the synthesis of NCs.

Automated summary

Pathway-dependent chirality control in silver nanoclusters is achieved by using enantiomeric ligand, leading to the formation of chiral silver nanoclusters with intrinsic chirality. Guest binding to the nanoclusters' shell can reverse the stability between right- and left-handed nanoclusters, resulting in unprecedented chirality inversion.