Alkynyl-Protected Chiral Bimetallic Ag₂₂ Cu₇ Superatom with Multiple Chirality Origins

Understanding the origin of chirality in the nanostructured materials is essential for chiroptical and catalytic applications. Here we report a chiral AgCu superatomic cluster, [Ag₂₂ Cu₇ (C≡CR)₁₆ (PPh₃ )₅ Cl₆ ](PPh₄ ), Ag₂₂ Cu₇ , protected by an achiral alkynyl ligand (HC≡CR: 3,5-bis(trifluoromethyl)phenylacetylene). Its crystal structure comprises a rare interpenetrating biicosahedral Ag₁₇ Cu₂ core, which is stabilized by four different types of motifs: one Cu(C≡CR)₂ , four -C≡CR, two chlorides and one helical Ag₅ Cu₄ (C≡CR)₁₀ (PPh₃ )₅ Cl₄ . Structural analysis reveals that Ag₂₂ Cu₇ exhibits multiple chirality origins, including the metal core, the metal-ligand interface and the ligand layer. Furthermore, the circular dichroism spectra of R/S-Ag₂₂ Cu₇ are obtained by employing appropriate chiral molecules as optical enrichment agents. DFT calculations show that Ag₂₂ Cu₇ is an eight-electron superatom, confirm that the cluster is chirally active, and help to analyze the origins of the circular dichroism.