Spontaneous Resolution of Chiral Multi-Thiolate-Protected Ag₃₀ Nanoclusters

Despite significant progress achieved in the preparation of chiral nanoparticles, the enantioseparation of racemates still presents a big challenge in nanomaterial research. Herein, we report the synthesis and structural characterization of racemic anisotropic nanocluster Ag₃₀(C₂B₁₀H₉S₃)₈Dppm₆ (Ag -rac), which is protected by mixed carboranetrithiolate and phosphine ligands. Spontaneous self-resolution of the racemates was realized through conglomerate crystallization in dimethylacetamide (DMAc). The homochiral nanoclusters in the racemic conglomerates adopt enantiomeric helical self-assemblies (R/L-Ag ). Diverse noncovalent interactions as the driving force in directing superstructure packing were elucidated in detail. Furthermore, the nanoclusters show red luminescence in both solid and solution states, and the racemic conglomerates display a mirror-image CPL response. This work provides atom-precise helical nanoparticle superstructures that facilitate an in-depth understanding of the helical-assembly mechanism.