A Chiral CdS Magic-Size Cluster with Enantiomerically-Biased Crystallization

• DOI: 10.1021/jacs.5c02549
• Publication Date: 2025-05-15T15:01:37Z
• Authors: Cheng Xu; Zhenyi Zhang; Zheng Zhou; Haixiang Han
• Keywords: Cluster size

Despite the symmetric, achiral atomic lattices typically found in binary semiconductor nanocrystals, we show that during their early formation stages, especially magic-size cluster (MSC) regime, chirality can be present these metastable, transient species, which are capable of further self-assembling into high-level chiral superstructures. Through a cation exchange process operating at room temperature, structurally symmetrical copper sulfide has been successfully converted pair enantiomeric cadmium MSCs, formulated as Cd28S17I22(PEt3)12 (abbreviated (+)/(-)-[Cd28S17]). The structures two MSCs were established by single-crystal X-ray crystallography. It is revealed [Cd28S17] feature an antisupertetrahedron configuration never observed reported CdS structures. Remarkably, rather than crystallizing racemic mixture, (+)/(-)-[Cd28S17] naturally crystallize out enantiomerically biased manner, sufficiently rendering distinctly opposite chiroptical responses. This behavior reflects genuine circular dichroism activity, directly attributed to structure this well-known quantum photonic nanomaterial.