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  • Title: Self-Regulated Pathway-Dependent Chirality Control of Silver Nanoclusters.
    Author: Nakashima T, Tanibe R, Yoshida H, Ehara M, Kuzuhara M, Kawai T.
    Journal: Angew Chem Int Ed Engl; 2022 Aug 22; 61(34):e202208273. PubMed ID: 35764534.
    Abstract:
    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, α-dihydrolipoic acid (DHLA), for the synthesis of Ag NCs leads to the preferential formation of one-handed chiral Ag29 (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.
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