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Updated: Jan 11, 2026
Spatial Separation of Molecular Conformers and Clusters
Published on: January 9, 2014
Cis-Trans Isomerism Revealed in Circularly Polarized Luminescent Superatomic Ag28 Nanoclusters
Jie Wang1,2, Meng-Wei He1, Yue Ma1
1Henan Key Laboratory of Crystalline Molecular Functional Materials, Key Laboratory of Special Functional Molecular Materials, Ministry of Education, College of Chemistry, Zhengzhou University, Zhengzhou, 450001, China.
Abstract:
Atomically precise metal nanoclusters facilitate the exploration of chiral origin in metal nanomaterials, meanwhile, their structural isomers with subtle variations serve as ideal models for investigating the structure-property relationship at the atomic level. Here, we obtained two pairs of chiral superatomic cis-trans isomers with the formula [R/S-Ag28(SOC10H15)14(CF3COO)10] (denoted as R/S-Ag28-cis/trans), where the cis and trans configurations coexist within the R and S chiral forms, respectively. Single crystal X-ray diffraction (SCXRD) analysis revealed that Ag28 clusters adopt a chiral core-shell configuration of Ag12@Ag14S12, consisting of an Ag12 kernel encapsulated within a chiral Ag14S12 cage. The additional two AgS units are located in a different fashion on the flanks of the framework, leading to the cis-trans isomerism of the silver clusters. DFT calculation reveals the distinctions in electronic structures and optical absorptions of the cis-trans isomers. The enantiomeric R/S-Ag28 exhibit intense red phosphorescence at 740 nm in the crystalline state, and hold a ∼28 nm blueshift in solution. Furthermore, R/S-Ag28 display circularly polarized luminescence (CPL) activity, achieving a maximum (|glum|) value of 1 × 10-3 in the crystalline state. This study enriches the diversity of chiral superatomic clusters and introduces cis-trans isomerism in metal clusters, establishing a novel platform to explore structure-activity relationships.
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