Solubility-Driven Isolation of a Metastable Nonagold Cluster with Body-Centered Cubic Structure

Hui Shen; Elli Selenius; Pengpeng Ruan; Xihua Li; Peng Yuan; Omar Lopez-Estrada; Sami Malola; Shuichao Lin; Boon K. Teo; Hannu Häkkinen; Nanfeng Zheng

doi:10.1002/chem.202001753

Solubility-Driven Isolation of a Metastable Nonagold Cluster with Body-Centered Cubic Structure

Hui Shen, Elli Selenius, Pengpeng Ruan, Xihua Li, Peng Yuan, Omar Lopez-Estrada, Sami Malola, Shuichao Lin, Boon K. Teo, Hannu Häkkinen^*, Nanfeng Zheng^*

^*Corresponding author for this work

Science Institute

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

10 Citations (Scopus)

Abstract

The conventional synthetic methodology for atomically precise gold nanoclusters by using reduction in solution offers only the thermodynamically most stable nanoclusters. Herein, a solubility-driven isolation strategy is reported to access a metastable gold cluster. The cluster, with the composition of [Au₉(PPh₃)₈]⁺ (1), displays an unusual, nearly perfect body-centered cubic (bcc) structure. As revealed by ESI-MS and UV/Vis measurements, the cluster is metastable in solution and converts to the well-known [Au₁₁(PPh₃)₈Cl₂]⁺ (2) within just 90 min. DFT calculations revealed that although both 1 and 2 are eight-electron superatoms, there is a driving force to convert 1 to 2 as shown by the increased cohesion and larger HOMO–LUMO energy gap of 2. The isolation and crystallization of the metastable gold cluster were achieved in a biphasic reaction system in which reduction of gold precursors and crystallization of 1 took place concurrently. This synthetic protocol represents a successful strategy for investigations of other metastable species in metal nanocluster chemistry.

Original language	English
Pages (from-to)	8465-8470
Number of pages	6
Journal	Chemistry - A European Journal
Volume	26
Issue number	38
DOIs	https://doi.org/10.1002/chem.202001753
Publication status	Published - 8 Jul 2020

Bibliographical note

Funding Information:
We thank the National Key R&D Program of China (2017YFA0207302) and the NSF of China (21890752, 21731005, 21721001) for financial support. The computational work by the University of Jyväskylä was supported by the Academy of Finland (grants 294217, 319208, 315549), and through H.H.’s Academy Professorship. H.H. acknowledges support from China's National Innovation and Intelligence Introduction Base visitor program. E.S. acknowledges the Emil Aaltonen Foundation for a PhD study grant. The computations were made at the CSC supercomputing center in Finland and as part of a PRACE project in the Barcelona Supercomputing Center.

Publisher Copyright:
© 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Other keywords

body-centered cubic
gold
metastable compounds
nanoclusters
solubility

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10.1002/chem.202001753

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@article{317b082d0fc44f9db3118e2391effdb1,

title = "Solubility-Driven Isolation of a Metastable Nonagold Cluster with Body-Centered Cubic Structure",

abstract = "The conventional synthetic methodology for atomically precise gold nanoclusters by using reduction in solution offers only the thermodynamically most stable nanoclusters. Herein, a solubility-driven isolation strategy is reported to access a metastable gold cluster. The cluster, with the composition of [Au9(PPh3)8]+ (1), displays an unusual, nearly perfect body-centered cubic (bcc) structure. As revealed by ESI-MS and UV/Vis measurements, the cluster is metastable in solution and converts to the well-known [Au11(PPh3)8Cl2]+ (2) within just 90 min. DFT calculations revealed that although both 1 and 2 are eight-electron superatoms, there is a driving force to convert 1 to 2 as shown by the increased cohesion and larger HOMO–LUMO energy gap of 2. The isolation and crystallization of the metastable gold cluster were achieved in a biphasic reaction system in which reduction of gold precursors and crystallization of 1 took place concurrently. This synthetic protocol represents a successful strategy for investigations of other metastable species in metal nanocluster chemistry.",

keywords = "body-centered cubic, gold, metastable compounds, nanoclusters, solubility",

author = "Hui Shen and Elli Selenius and Pengpeng Ruan and Xihua Li and Peng Yuan and Omar Lopez-Estrada and Sami Malola and Shuichao Lin and Teo, {Boon K.} and Hannu H{\"a}kkinen and Nanfeng Zheng",

note = "Funding Information: We thank the National Key R&D Program of China (2017YFA0207302) and the NSF of China (21890752, 21731005, 21721001) for financial support. The computational work by the University of Jyv{\"a}skyl{\"a} was supported by the Academy of Finland (grants 294217, 319208, 315549), and through H.H.{\textquoteright}s Academy Professorship. H.H. acknowledges support from China's National Innovation and Intelligence Introduction Base visitor program. E.S. acknowledges the Emil Aaltonen Foundation for a PhD study grant. The computations were made at the CSC supercomputing center in Finland and as part of a PRACE project in the Barcelona Supercomputing Center. Publisher Copyright: {\textcopyright} 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim",

year = "2020",

month = jul,

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doi = "10.1002/chem.202001753",

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AU - Shen, Hui

AU - Selenius, Elli

AU - Ruan, Pengpeng

AU - Li, Xihua

AU - Yuan, Peng

AU - Lopez-Estrada, Omar

AU - Malola, Sami

AU - Lin, Shuichao

AU - Teo, Boon K.

AU - Häkkinen, Hannu

AU - Zheng, Nanfeng

N1 - Funding Information: We thank the National Key R&D Program of China (2017YFA0207302) and the NSF of China (21890752, 21731005, 21721001) for financial support. The computational work by the University of Jyväskylä was supported by the Academy of Finland (grants 294217, 319208, 315549), and through H.H.’s Academy Professorship. H.H. acknowledges support from China's National Innovation and Intelligence Introduction Base visitor program. E.S. acknowledges the Emil Aaltonen Foundation for a PhD study grant. The computations were made at the CSC supercomputing center in Finland and as part of a PRACE project in the Barcelona Supercomputing Center. Publisher Copyright: © 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

PY - 2020/7/8

Y1 - 2020/7/8

N2 - The conventional synthetic methodology for atomically precise gold nanoclusters by using reduction in solution offers only the thermodynamically most stable nanoclusters. Herein, a solubility-driven isolation strategy is reported to access a metastable gold cluster. The cluster, with the composition of [Au9(PPh3)8]+ (1), displays an unusual, nearly perfect body-centered cubic (bcc) structure. As revealed by ESI-MS and UV/Vis measurements, the cluster is metastable in solution and converts to the well-known [Au11(PPh3)8Cl2]+ (2) within just 90 min. DFT calculations revealed that although both 1 and 2 are eight-electron superatoms, there is a driving force to convert 1 to 2 as shown by the increased cohesion and larger HOMO–LUMO energy gap of 2. The isolation and crystallization of the metastable gold cluster were achieved in a biphasic reaction system in which reduction of gold precursors and crystallization of 1 took place concurrently. This synthetic protocol represents a successful strategy for investigations of other metastable species in metal nanocluster chemistry.

AB - The conventional synthetic methodology for atomically precise gold nanoclusters by using reduction in solution offers only the thermodynamically most stable nanoclusters. Herein, a solubility-driven isolation strategy is reported to access a metastable gold cluster. The cluster, with the composition of [Au9(PPh3)8]+ (1), displays an unusual, nearly perfect body-centered cubic (bcc) structure. As revealed by ESI-MS and UV/Vis measurements, the cluster is metastable in solution and converts to the well-known [Au11(PPh3)8Cl2]+ (2) within just 90 min. DFT calculations revealed that although both 1 and 2 are eight-electron superatoms, there is a driving force to convert 1 to 2 as shown by the increased cohesion and larger HOMO–LUMO energy gap of 2. The isolation and crystallization of the metastable gold cluster were achieved in a biphasic reaction system in which reduction of gold precursors and crystallization of 1 took place concurrently. This synthetic protocol represents a successful strategy for investigations of other metastable species in metal nanocluster chemistry.

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DO - 10.1002/chem.202001753

M3 - Article

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SN - 0947-6539

VL - 26

SP - 8465

EP - 8470

JO - Chemistry - A European Journal

JF - Chemistry - A European Journal

IS - 38

ER -

Solubility-Driven Isolation of a Metastable Nonagold Cluster with Body-Centered Cubic Structure

Abstract

Bibliographical note

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