Hydride Doping Effects on the Structure and Properties of Eight-Electron Rh/Ag Superatoms: The [RhHx@Ag21-x{S2P(OnPr)2}12] (x = 0-2) Series

Tzu Hao Chiu; Jian Hong Liao; Ying Yann Wu; Jie Ying Chen; Yuan Jang Chen; Xiaoping Wang; Samia Kahlal; Jean Yves Saillard; C. W. Liu

doi:10.1021/jacs.3c04482

Hydride Doping Effects on the Structure and Properties of Eight-Electron Rh/Ag Superatoms: The [RhH_x@Ag_21-x{S₂P(OⁿPr)₂}₁₂] (x = 0-2) Series

Tzu Hao Chiu, Jian Hong Liao, Ying Yann Wu, Jie Ying Chen, Yuan Jang Chen, Xiaoping Wang, Samia Kahlal, Jean Yves Saillard, C. W. Liu

Single Crystal Diffraction

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

9 Scopus citations

Abstract

Three hitherto unknown eight-electron rhodium/silver alloy nanoclusters, [RhAg₂₁{S₂P(OⁿPr)₂}₁₂] (1), [RhHAg₂₀{S₂P(OⁿPr)₂}₁₂] (2), and [RhH₂Ag₁₉{S₂P(OⁿPr)₂}₁₂] (3), have been isolated and fully characterized. Cluster 1 contains a regular Rh@Ag₁₂ icosahedral core, whereas 2 and 3 exhibit distorted RhH@Ag₁₂ and RhH₂@Ag₁₂ icosahedral cores. The single-crystal neutron structure of 2 located the encapsulated hydride at the center of an enlarged RhAg₃ tetrahedron. A similar position was found by neutron diffraction for one of the hydrides in 3, whereas the other hydride is trigonally coordinated to Rh and an elongated Ag-Ag edge. The solid-state structures of 1-3 possess C₁ symmetry due to the asymmetric arrangement of the surrounding capping Ag atoms. Our investigation shows that the insertion of one hydride dopant provokes the elimination of one capping silver atom on the cluster surface, resulting in the general formula [RhH_x@Ag_21-x{S₂P(OⁿPr)₂}₁₂] (x = 0-2), which maintains the same number of cluster electrons as well as neutral charge. Clusters 1-3 exhibit an intense emission band in the NIR region. Contrarily to their PdAg₂₁ and PdHAg₂₀ relatives, the 4d orbitals of the encapsulated heterometal are somewhat involved in the optical processes.

Original language	English
Pages (from-to)	16739-16747
Number of pages	9
Journal	Journal of the American Chemical Society
Volume	145
Issue number	30
DOIs	https://doi.org/10.1021/jacs.3c04482
State	Published - Aug 2 2023

Funding

This work was supported by the National Science and Technology Council of Taiwan (NSTC 111-2113-M-259-002) and the GENCI French National Computer Resource Center (A0030807367). We thank Dr. R. Marchal for computational help. Single-crystal neutron diffraction performed on TOPAZ used resources at the Spallation Neutron Source, a DOE Office of Science User Facility operated by the Oak Ridge National Laboratory, under contract no. DE-AC05-00OR22725 with UT-Battelle, LLC. We thank the Instrumentation Center of National Taiwan Normal University (NSTC 111-2731-M-003-001) and Academia Sinica High-Field NMR Center (HFNMRC) for technical support; HFNMRC is funded by Academia Sinica Core Facility and Innovative Instrument Project (AS-CFII-111-214).

Access to Document

10.1021/jacs.3c04482

Cite this

@article{9d4a4c06919e4d68a4525f7ded967e6e,

title = "Hydride Doping Effects on the Structure and Properties of Eight-Electron Rh/Ag Superatoms: The [RhHx@Ag21-x{S2P(OnPr)2}12] (x = 0-2) Series",

abstract = "Three hitherto unknown eight-electron rhodium/silver alloy nanoclusters, [RhAg21{S2P(OnPr)2}12] (1), [RhHAg20{S2P(OnPr)2}12] (2), and [RhH2Ag19{S2P(OnPr)2}12] (3), have been isolated and fully characterized. Cluster 1 contains a regular Rh@Ag12 icosahedral core, whereas 2 and 3 exhibit distorted RhH@Ag12 and RhH2@Ag12 icosahedral cores. The single-crystal neutron structure of 2 located the encapsulated hydride at the center of an enlarged RhAg3 tetrahedron. A similar position was found by neutron diffraction for one of the hydrides in 3, whereas the other hydride is trigonally coordinated to Rh and an elongated Ag-Ag edge. The solid-state structures of 1-3 possess C1 symmetry due to the asymmetric arrangement of the surrounding capping Ag atoms. Our investigation shows that the insertion of one hydride dopant provokes the elimination of one capping silver atom on the cluster surface, resulting in the general formula [RhHx@Ag21-x{S2P(OnPr)2}12] (x = 0-2), which maintains the same number of cluster electrons as well as neutral charge. Clusters 1-3 exhibit an intense emission band in the NIR region. Contrarily to their PdAg21 and PdHAg20 relatives, the 4d orbitals of the encapsulated heterometal are somewhat involved in the optical processes.",

author = "Chiu, {Tzu Hao} and Liao, {Jian Hong} and Wu, {Ying Yann} and Chen, {Jie Ying} and Chen, {Yuan Jang} and Xiaoping Wang and Samia Kahlal and Saillard, {Jean Yves} and Liu, {C. W.}",

note = "Publisher Copyright: {\textcopyright} 2023 American Chemical Society.",

year = "2023",

month = aug,

day = "2",

doi = "10.1021/jacs.3c04482",

language = "English",

volume = "145",

pages = "16739--16747",

journal = "Journal of the American Chemical Society",

issn = "0002-7863",

publisher = "American Chemical Society",

number = "30",

}

TY - JOUR

T1 - Hydride Doping Effects on the Structure and Properties of Eight-Electron Rh/Ag Superatoms

T2 - The [RhHx@Ag21-x{S2P(OnPr)2}12] (x = 0-2) Series

AU - Chiu, Tzu Hao

AU - Liao, Jian Hong

AU - Wu, Ying Yann

AU - Chen, Jie Ying

AU - Chen, Yuan Jang

AU - Wang, Xiaoping

AU - Kahlal, Samia

AU - Saillard, Jean Yves

AU - Liu, C. W.

PY - 2023/8/2

Y1 - 2023/8/2

N2 - Three hitherto unknown eight-electron rhodium/silver alloy nanoclusters, [RhAg21{S2P(OnPr)2}12] (1), [RhHAg20{S2P(OnPr)2}12] (2), and [RhH2Ag19{S2P(OnPr)2}12] (3), have been isolated and fully characterized. Cluster 1 contains a regular Rh@Ag12 icosahedral core, whereas 2 and 3 exhibit distorted RhH@Ag12 and RhH2@Ag12 icosahedral cores. The single-crystal neutron structure of 2 located the encapsulated hydride at the center of an enlarged RhAg3 tetrahedron. A similar position was found by neutron diffraction for one of the hydrides in 3, whereas the other hydride is trigonally coordinated to Rh and an elongated Ag-Ag edge. The solid-state structures of 1-3 possess C1 symmetry due to the asymmetric arrangement of the surrounding capping Ag atoms. Our investigation shows that the insertion of one hydride dopant provokes the elimination of one capping silver atom on the cluster surface, resulting in the general formula [RhHx@Ag21-x{S2P(OnPr)2}12] (x = 0-2), which maintains the same number of cluster electrons as well as neutral charge. Clusters 1-3 exhibit an intense emission band in the NIR region. Contrarily to their PdAg21 and PdHAg20 relatives, the 4d orbitals of the encapsulated heterometal are somewhat involved in the optical processes.

AB - Three hitherto unknown eight-electron rhodium/silver alloy nanoclusters, [RhAg21{S2P(OnPr)2}12] (1), [RhHAg20{S2P(OnPr)2}12] (2), and [RhH2Ag19{S2P(OnPr)2}12] (3), have been isolated and fully characterized. Cluster 1 contains a regular Rh@Ag12 icosahedral core, whereas 2 and 3 exhibit distorted RhH@Ag12 and RhH2@Ag12 icosahedral cores. The single-crystal neutron structure of 2 located the encapsulated hydride at the center of an enlarged RhAg3 tetrahedron. A similar position was found by neutron diffraction for one of the hydrides in 3, whereas the other hydride is trigonally coordinated to Rh and an elongated Ag-Ag edge. The solid-state structures of 1-3 possess C1 symmetry due to the asymmetric arrangement of the surrounding capping Ag atoms. Our investigation shows that the insertion of one hydride dopant provokes the elimination of one capping silver atom on the cluster surface, resulting in the general formula [RhHx@Ag21-x{S2P(OnPr)2}12] (x = 0-2), which maintains the same number of cluster electrons as well as neutral charge. Clusters 1-3 exhibit an intense emission band in the NIR region. Contrarily to their PdAg21 and PdHAg20 relatives, the 4d orbitals of the encapsulated heterometal are somewhat involved in the optical processes.

UR - http://www.scopus.com/inward/record.url?scp=85166387278&partnerID=8YFLogxK

U2 - 10.1021/jacs.3c04482

DO - 10.1021/jacs.3c04482

M3 - Article

C2 - 37473452

AN - SCOPUS:85166387278

SN - 0002-7863

VL - 145

SP - 16739

EP - 16747

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 30

ER -

Hydride Doping Effects on the Structure and Properties of Eight-Electron Rh/Ag Superatoms: The [RhH_x@Ag_21-x{S₂P(OⁿPr)₂}₁₂] (x = 0-2) Series

Abstract

Funding

Access to Document

Other files and links

Fingerprint

Cite this