Assembly of Luminescent Chiral Gold(I)-Sulfido Clusters via Chiral Self-Sorting

Due to the ubiquity of chirality in nature, chiral self-assembly involving self-sorting behaviors has remained as one of the most important research topics of interests. Herein, starting from a racemic mixture of SEG-based (SEG=SEGPHOS) chlorogold(I) precursors, a unique chiral butterfly-shape hexadecanuclear gold(I) cluster (Au₁₆) with different ratios of R^SEG and S^SEG ligands is obtained via homoleptic and heterochiral self-sorting. More interestingly, by employing different chlorogold(I) precursors of opposite chirality (such as R^SEG-Au₂ and S^BIN-Au₂ (BIN=BINAP)), an unprecedented heteroleptic and heterochiral self-sorting strategy has been developed to give a series of heteroleptic chiral decanuclear gold(I) clusters (Au₁₀) with propellor-shape structures. Heterochiral and heteroleptic self-sorting have also been observed between enantiomers of homoleptic chiral Au₁₀ clusters to result in the heteroleptic chiral Au₁₀ clusters via cluster-to-cluster transformation. Incorporation of heteroleptic ligands is found to decrease the symmetry from S₄ of homoleptic meso Au₁₀ to C₂ of heteroleptic chiral Au₁₀ clusters. The chirality has been transferred from the axial chiral ligands and stored in the heteroleptic gold(I) clusters.