Extra Silver Atom Triggers Room‐Temperature Photoluminescence in Atomically Precise Radarlike Silver Clusters

• Published in: Angewandte Chemie International Edition Vol. 59; no. 29; pp. 11898 - 11902
• Main Authors: Yang, Jin‐Sen, Han, Zhen, Dong, Xi‐Yan, Luo, Peng, Mo, Hui‐Lin, Zang, Shuang‐Quan
• Format: Journal Article
• Language: English
• Published: Germany Wiley Subscription Services, Inc 13.07.2020
• Edition: International ed. in English
• Subjects: atomic precision; cluster compounds; Emission; Luminescence; Metal clusters; Metals; Photoluminescence; Photons; Rigidity; Room temperature; Silver; cluster compounds; silver; atomic precision; luminescence; photoluminescence
• ISSN: 1433-7851; 1521-3773
• DOI: 10.1002/anie.202004268

Luminescent metal clusters show promise for applications in imaging and sensing. However, promoting emission from metal clusters at room temperature is a challenging task owing to the lack of an efficient approach to suppress the nonradiative decay process in metal cores. We report herein that the addition of a silver atom into a metal interstice of the radarlike thiolated silver cluster [Ag27(StBu)14(S)2(CF3COO)9(DMAc)4]⋅DMAc (NC1, DMAc=dimethylacetamide), which is non‐emissive under ambient conditions, produced another silver cluster [Ag28(AdmS)14(S)2(CF3COO)10(H2O)4] (NC2) that displayed bright green room‐temperature photoluminescence aided by the new ligand 1‐adamantanethiol (AdmSH). The 28th Ag atom, which hardly affects the geometrical and electronic structures of the Ag–S skeleton, triggered the emission of green light as a result of the rigidity of the cluster structure. Magic number 28: A 28th silver atom combined with a more rigid thiolate ligand led to room‐temperature photoluminescence in radarlike silver clusters possessing similar geometrical and electronic structures (see picture). The additional silver atom triggered the emission of green light as a result of the rigidity of the cluster structure.