Elucidating the Doping Effect on the Electronic Structure of Thiolate‐Protected Silver Superatoms by Photoelectron Spectroscopy

Gas‐phase photoelectron spectroscopy (PES) was conducted on [XAg24(SPhMe2)18]− (X=Ag, Au) and [YAg24(SPhMe2)18]2− (Y=Pd, Pt), which have a formal superatomic core (X@Ag12)5+ or (Y@Ag12)4+ with icosahedral symmetry. PES results show that superatomic orbitals in the (Au@Ag12)5+ core remain unshifted w...

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Bibliographic Details
Published in:Angewandte Chemie International Edition 2019-08, Vol.58 (34), p.11637-11641
Main Authors: Kim, Kuenhee, Hirata, Keisuke, Nakamura, Katsunosuke, Kitazawa, Hirokazu, Hayashi, Shun, Koyasu, Kiichirou, Tsukuda, Tatsuya
Format: Article
Language:English
Subjects:
Anion photoelectron spectroscopy
Doping
doping effects
Electronic structure
Electrons
Gold
Icosahedral phase
multiply charged anions
Orbitals
Organic chemistry
Palladium
Photoelectron spectroscopy
Photoelectrons
Platinum
repulsive Coulomb barrier
Silver
Spectroscopy
Spectrum analysis
thiolate-protected silver cluster
Vacuum
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Summary:Gas‐phase photoelectron spectroscopy (PES) was conducted on [XAg24(SPhMe2)18]− (X=Ag, Au) and [YAg24(SPhMe2)18]2− (Y=Pd, Pt), which have a formal superatomic core (X@Ag12)5+ or (Y@Ag12)4+ with icosahedral symmetry. PES results show that superatomic orbitals in the (Au@Ag12)5+ core remain unshifted with respect to those in the (Ag@Ag12)5+ core, whereas the orbitals in the (Y@Ag12)4+ (Y = Pd, Pt) core shift up in energy by about 1.4 eV. The remarkable doping effect of a single Y atom (Y=Pd, Pt) on the electronic structure of the chemically modified (Ag@Ag12)5+ superatom was reproduced by theoretical calculations on simplified model systems and was ascribed to 1) the weaker binding of valence electrons in Y@(Ag+)12 compared to Ag+@(Ag+)12 due to the reduction in formal charge of the core potential, and 2) the upward shift of the apparent vacuum level due to the presence of a repulsive Coulomb barrier between [YAg24(SPhMe2)18]− and electron. Central exchange: The heteroatom doping effect on superatomic orbitals in [XAg24(SR)18]− (X=Ag, Au) and [YAg24(SR)18]2− (Y=Pd, Pt) was examined using gas‐phase photoelectron spectroscopy. The adiabatic electron affinity of [XAg24(SR)18] is reduced by approximately 1.4 eV upon replacement of the central X+ cation by a neutral Y atom.
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.201901750