Superatom‐in‐Superatom Nanoclusters: Synthesis, Structure, and Photoluminescence

• Published in: Angewandte Chemie International Edition 2023-08, Vol.62 (33), p.e202302591-n/a
• Main Authors: Yi, Hanseok, Song, Suhwan, Han, Sang Myeong, Lee, Jieun, Kim, Woojae, Sim, Eunji, Lee, Dongil
• Format: Article
• Language: English
• Subjects: Dopants; Doping; Electron affinity; Luminescence; Metal Hydride; Metal hydrides; Metals; Nanoclusters; Open d-Shell; Photoluminescence; Photons; Silver Nanocluster; Superatom
• ISSN: 1433-7851; 1521-3773
• DOI: 10.1002/anie.202302591

We report a new strategy in which a thiolate‐protected Ag25 nanocluster can be doped with open d‐shell group 8 (Ru, Os) and 9 (Ir) metals by forming metal hydride (RuH2, OsH2, IrH) superatoms with a closed d‐shell. Structural analyses using various experimental and theoretical methods revealed that the Ag25 nanoclusters were co‐doped with the open d‐shell metal and hydride species to produce superatom‐in‐superatom nanoclusters, establishing a novel superatom doping phenomenon for open d‐shell metals. The synthesized superatom‐in‐superatom nanoclusters exhibited dopant‐dependent photoluminescence (PL) properties. Comparative PL lifetime studies of the Ag25 nanoclusters doped with 8–10 group metals revealed that both radiative and nonradiative processes were significantly dependent on the dopant. The former is strongly correlated with the electron affinity of the metal dopant, whereas the latter is governed predominantly by the kernel structure changed upon the doping of the metal hydride(s). The doping of group 8 and 9 metals having unpaired d electrons into a thiolate‐protected Ag25 nanocluster was demonstrated. Open d‐shell group 8 (Ru, Os) and 9 (Rh, Ir) metal atoms could be incorporated into the Ag24(SR)18 superatomic framework by forming metal‐hydride superatoms with a closed d‐shell. The synthesized superatom‐in‐superatom nanoclusters exhibited dopant‐dependent photoluminescence intensities and lifetimes.