Superatom-in-Superatom [RhH@Ag24(SPhMe2)18]2− Nanocluster

Hanseok Yi; Sang Myeong Han; Suhwan Song; Minseok Kim; Eunji Sim; Dongil Lee

doi:10.1002/anie.202106311

Superatom-in-Superatom [RhH@Ag₂₄(SPhMe₂)₁₈]²⁻ Nanocluster

Hanseok Yi, Sang Myeong Han, Suhwan Song, Minseok Kim, Eunji Sim, Dongil Lee

Department of Chemistry

Research output: Contribution to journal › Article › peer-review

8 Citations (Scopus)

Abstract

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 [RhHAg₂₄(SPhMe₂)₁₈]²⁻ nanocluster, in which a Rh atom with open d-shells ([Kr]4d⁸5s¹) is incorporated into the Ag₂₄ framework by forming a RhH superatom with closed d-shells ([Kr]4d¹⁰). Combined experimental and theoretical investigations showed that the Ag₂₄ 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 [RhHAg₂₄(SPhMe₂)₁₈]²⁻ nanocluster was isoelectronic to the [PdAg₂₄(SPhMe₂)₁₈]²⁻ nanocluster with the superatomic 8-electron configuration (1S²1P⁶). 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.

Original language	English
Pages (from-to)	22293-22300
Number of pages	8
Journal	Angewandte Chemie - International Edition
Volume	60
Issue number	41
DOIs	https://doi.org/10.1002/anie.202106311
Publication status	Published - 2021 Oct 4

Bibliographical note

Funding Information:
D.L. acknowledges the support provided by the National Research Foundation of Korea (NRF; grant No. NRF-2017R1A2B3006651) and the Carbon-to-X Project (Project No. 2020M3H7A1096344) through the NRF funded by the Ministry of Science and ICT, Republic of Korea. E.S. acknowledges the support provided by the NRF grant (NRF-2020R1A2C2007468). This work was also partially supported by MSIT and the Pohang Accelerator Laboratory (PAL), Korea. The authors acknowledge the PAL for the beam line use (2020-2nd-2D-044 and 2020-3rd-2D-020).

Funding Information:
D.L. acknowledges the support provided by the National Research Foundation of Korea (NRF; grant No. NRF‐2017R1A2B3006651) and the Carbon‐to‐X Project (Project No. 2020M3H7A1096344) through the NRF funded by the Ministry of Science and ICT, Republic of Korea. E.S. acknowledges the support provided by the NRF grant (NRF‐2020R1A2C2007468). This work was also partially supported by MSIT and the Pohang Accelerator Laboratory (PAL), Korea. The authors acknowledge the PAL for the beam line use (2020‐2nd‐2D‐044 and 2020‐3rd‐2D‐020).

Publisher Copyright:
© 2021 Wiley-VCH GmbH

All Science Journal Classification (ASJC) codes

Catalysis
Chemistry(all)

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10.1002/anie.202106311

Cite this

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title = "Superatom-in-Superatom [RhH@Ag24(SPhMe2)18]2− Nanocluster",

abstract = "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 [RhHAg24(SPhMe2)18]2− nanocluster, in which a Rh atom with open d-shells ([Kr]4d85s1) is incorporated into the Ag24 framework by forming a RhH superatom with closed d-shells ([Kr]4d10). Combined experimental and theoretical investigations showed that the Ag24 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 [RhHAg24(SPhMe2)18]2− nanocluster was isoelectronic to the [PdAg24(SPhMe2)18]2− nanocluster with the superatomic 8-electron configuration (1S21P6). 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.",

author = "Hanseok Yi and Han, {Sang Myeong} and Suhwan Song and Minseok Kim and Eunji Sim and Dongil Lee",

note = "Funding Information: D.L. acknowledges the support provided by the National Research Foundation of Korea (NRF; grant No. NRF-2017R1A2B3006651) and the Carbon-to-X Project (Project No. 2020M3H7A1096344) through the NRF funded by the Ministry of Science and ICT, Republic of Korea. E.S. acknowledges the support provided by the NRF grant (NRF-2020R1A2C2007468). This work was also partially supported by MSIT and the Pohang Accelerator Laboratory (PAL), Korea. The authors acknowledge the PAL for the beam line use (2020-2nd-2D-044 and 2020-3rd-2D-020). Funding Information: D.L. acknowledges the support provided by the National Research Foundation of Korea (NRF; grant No. NRF‐2017R1A2B3006651) and the Carbon‐to‐X Project (Project No. 2020M3H7A1096344) through the NRF funded by the Ministry of Science and ICT, Republic of Korea. E.S. acknowledges the support provided by the NRF grant (NRF‐2020R1A2C2007468). This work was also partially supported by MSIT and the Pohang Accelerator Laboratory (PAL), Korea. The authors acknowledge the PAL for the beam line use (2020‐2nd‐2D‐044 and 2020‐3rd‐2D‐020). Publisher Copyright: {\textcopyright} 2021 Wiley-VCH GmbH",

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AU - Kim, Minseok

AU - Sim, Eunji

AU - Lee, Dongil

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N2 - 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 [RhHAg24(SPhMe2)18]2− nanocluster, in which a Rh atom with open d-shells ([Kr]4d85s1) is incorporated into the Ag24 framework by forming a RhH superatom with closed d-shells ([Kr]4d10). Combined experimental and theoretical investigations showed that the Ag24 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 [RhHAg24(SPhMe2)18]2− nanocluster was isoelectronic to the [PdAg24(SPhMe2)18]2− nanocluster with the superatomic 8-electron configuration (1S21P6). 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.

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