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Superatom‐in‐Superatom [RhH@Ag 24 (SPhMe 2 ) 18 ] 2− Nanocluster
Author(s) -
Yi Hanseok,
Han Sang Myeong,
Song Suhwan,
Kim Minseok,
Sim Eunji,
Lee Dongil
Publication year - 2021
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.202106311
Subject(s) - superatom , nanoclusters , dopant , doping , chemistry , atom (system on chip) , crystallography , nanotechnology , atomic physics , materials science , chemical physics , electronic structure , computational chemistry , physics , optoelectronics , computer science , embedded system
Heterometal doping is a powerful method for tuning the physicochemical properties of metal nanoclusters. While the heterometals doped into such nanoclusters predominantly include transition metals with closed d‐shells, the doping of open d‐shell metals remains largely unexplored. Herein, we report the first synthesis of a [RhHAg 24 (SPhMe 2 ) 18 ] 2− nanocluster, in which a Rh atom with open d‐shells ([Kr]4d 8 5s 1 ) is incorporated into the Ag 24 framework by forming a RhH superatom with closed d‐shells ([Kr]4d 10 ). Combined experimental and theoretical investigations showed that the Ag 24 framework was co‐doped with Rh and hydride and that the RhH dopant was a superatomic construct of a Pd atom. Additional studies demonstrated that the [RhHAg 24 (SPhMe 2 ) 18 ] 2− nanocluster was isoelectronic to the [PdAg 24 (SPhMe 2 ) 18 ] 2− nanocluster with the superatomic 8‐electron configuration (1S 2 1P 6 ). This study demonstrated for the first time that a superatom could be incorporated into a cluster superatom to generate a stable superatom‐in‐superatom nanocluster.