Chiral Separation of Copper Sulfide [S–Cu<sub>36</sub>] Nanocluster Using a Chiral Adaptive Counterion
Yumeng Guo, Zhenyi Zhang, Haixiang Han, Zheng Zhou
Abstract
This work presents a new strategy to achieve the growth of copper sulfide nanoclusters with high nuclearity. Through a phosphine-assisted C–S reductive cleavage approach, an intrinsically chiral [Cu 4 ] cluster passes through a [S–Cu 9 ] cluster and transforms into a higher-nuclearity [S–Cu 36 ] cluster, which features a core–shell structure with a [Cu 4 ] 4+ core encapsulated by a chiral [Cu 20 S 12 ] shell. Interestingly, the spiral arrangement of the bidental ligands on the surface of the [S–Cu 36 ] cluster leads to the L- / R -enantiomeric configurations. Moreover, by utilization of [Na(THF) 6 ] + as a chiral adaptive counterion, [S–Cu 36 ] can be interlocked separately, thus enabling the isolation of homochiral clusters. Theoretical calculation suggests that the configuration transition between two enantiomeric [Na(THF) 6 ] + species is favorable at room temperature, thereby promoting the cocrystallization of resulting chiral products. This study introduces a novel perspective on the synthesis of chiral copper sulfide nanoclusters and presents an innovative approach to achieving the chiral separation of nanoclusters.