Atomically precise copper sulfide nanoclusters (Cu-S NCs) are of great interest, yet research on their controllable synthesis methods and luminescent properties remains limited. Herein, we report the syntheses and structures of two novel Cu-S NCs: Cu20S(AT)8(dppm)4(H)8(ClO4)2 (Cu20-H) and Cu20S3(AT)12(dppm)2(ClO4)2 (Cu20-S), (HAT = 1-adamantanethiol, dppm = bis(diphenylphosphino)methane), with Cu20-S being the first Cu-S NCs prepared via a sulfide-release approach involving thioacetamide. Both clusters exhibit unique structures with regiospecific organic surface coverage: dppm ligands are distributed at both ends of Cu20-H and at one end of Cu20-S. The core of Cu20-H is chiral with D2 symmetry, whereas the core of Cu20-S exhibits only mirror symmetry. Cu20-H is nearly nonemissive, while Cu20-S exhibits orange luminescence with a high photoluminescence quantum yield (PLQY) of 23.54% and a long lifetime of 10.08 μs at room temperature. The boost in the brightness of Cu20-S can be attributed to its rigid and polar structure, which results from the additional sulfide ions. This work presents a novel approach for constructing Cu-S NCs, enriches the copper cluster family, and provides insights into the luminescent properties of Cu-S NCs.
Jiang et al. (Mon,) studied this question.