Chiral Hydride Cu18 Clusters Transform to Superatomic Cu15Ag4 Clusters: Circularly Polarized Luminescence Lighting

The manipulation of metal cluster enantiomers and their reconstruction remain challenging. Here, for the first time, we report an enantiomeric pair of hydride copper clusters [Cu₁₈H(R/S-PEA)₁₂](BF₄)₅ (R/S-Cu₁₈H) made using designed chiral ligands. By manipulation of R/S-Cu₁₈H with Ag⁺ ions, H^- ions are released, leading to the reconstruction of 15 Cu atoms. Moreover, 4 Ag atoms replaced Cu atoms at the specific sites, resulting in the formation of homochiral [Cu₁₅Ag₄(R/S-PEA)₁₂](BF₄)₅ (R/S-Cu₁₅Ag₄) with an isomorphic metal skeleton. This process was accompanied by a reduction reaction generating two free valence elections in the chiral alloying counterparts, which displayed orange emission. The solid-state R/S-Cu₁₅Ag₄ exhibited a photoluminescence quantum yield of 7.02% and excellent circularly polarized luminescence. The chiral transformations were resolved by single-crystal X-ray diffraction. The development of chiral copper hydride precursor-based metal clusters with chiroptical activities holds tremendous promise for advancing the field of optoelectronics and enabling new applications in lighting, displays, and beyond.