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Observable but Not Isolable: The RhAu 24 (PET) 18 1+ Nanocluster
Author(s) -
Anderson Ian D.,
Riskowski Ryan A.,
Ackerson Christopher J.
Publication year - 2021
Publication title -
small
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 3.785
H-Index - 236
eISSN - 1613-6829
pISSN - 1613-6810
DOI - 10.1002/smll.202004078
Subject(s) - nanoclusters , rhodium , chemistry , x ray photoelectron spectroscopy , cluster (spacecraft) , crystallography , materials science , nanotechnology , physics , catalysis , organic chemistry , nuclear magnetic resonance , computer science , programming language
Abstract The synthesis and characterization of RhAu 24 (PET) 18 (PET = 2‐phenylethanethiol) is described. The cluster is cosynthesized with Au 25 (PET) 18 and rhodium thiolates in a coreduction of RhCl 3 , HAuCl 4 , and PET. Rapid decomposition of RhAu 24 (PET) 18 occurs when purified from the other reaction products, precluding the study of isolated cluster. Mixtures containing RhAu 24 (PET) 18 , Au 25 (PET) 18 , and rhodium thiolates are therefore characterized. Mass spectrometry, X‐ray photoelectron spectroscopy, and chromatography methods suggest a combination of charge–charge and metallophilic interactions among Au 25 (PET) 18 1− , rhodium thiolates and RhAu 24 (PET) 18 resulting in stabilization of RhAu 24 (PET) 18 . The charge of RhAu 24 (PET) 18 is assigned as 1+ on the basis of its stoichiometric 1:1 presence with anionic Au 25 (PET) 18 , and its stability is contextualized within the superatom electron counting rules. This analysis concludes that the Rh atom absorbs one superatomic electron to close its d‐shell, giving RhAu 24 (PET) 18 1+ a superatomic electron configuration of 1S 2 1P 4 . Overall, an updated framework for rationalizing open d‐shell heterometal dopant electronics in thiolated gold nanoclusters emerges.