Atomically Precise Enantiopure Bimetallic Janus Clusters.

Abstract

Asymmetric bimetallic Janus nanocrystals with a side-by-side interface have unique properties and important applications. However, understanding their fundamental issues, including their formation mechanism, interfacial linkage, and related properties, remains challenging, as does the preparation of enantiopure samples. Atomically precise Janus bimetal nanoclusters would unequivocally resolve these issues, yet they have not been realized. Here, based on Au and transition metals (Cu/Cd), and employing an S/P biligand strategy, we prepare and structurally resolve four Janus nanoclusters, including racemate 6e Au8/Cu4, 6e R-/S-Au8/Cu4 enantiomers, and 2e racemateAu3/Cd. Their interfacial linkage is unambiguously resolved at the atomic level, superatomic orbital splitting emerges, and unique molecule-like electronic transitions and chiroptical properties are present; more importantly, the dipolar distribution of bicomponents leads to a maximum dipole moment of up to 45 D, which drives the formation of 1D nanowires through self-assembly. This work provides a fundamental knowledge of intermetallic nanomaterials and an avenue for the synthesis of Janus nanoclusters.