Mechanistic Study of the Hydride Migration-Induced Reversible Isomerization in Au22(SR)15H Isomers

Qinzhen Li; Yesen Tan; Baoyu Huang; Sha Yang; Jinsong Chai; Xiaoping Wang; Yong Pei; Manzhou Zhu

doi:10.1021/jacs.3c02768

Mechanistic Study of the Hydride Migration-Induced Reversible Isomerization in Au₂₂(SR)₁₅H Isomers

Qinzhen Li, Yesen Tan, Baoyu Huang, Sha Yang, Jinsong Chai, Xiaoping Wang, Yong Pei, Manzhou Zhu

Single Crystal Diffraction

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

22 Scopus citations

Abstract

Unraveling the evolution mechanism of metal nanoclusters is of great importance in understanding the formation and evolution of metallic condensed matters. In this work, the specific evolution process between a pair of gold nanocluster (Au NC) isomers is completely revealed by introducing hydride ligands to simplify the research system. A hydride-containing Au NC, Au₂₂(SR)₁₅H, was synthesized by kinetic control, and the positions of the hydrides were then confirmed by combining X-ray diffraction, neutron diffraction, and DFT calculations. Importantly, a reversible structural isomerization was found to occur on this Au₂₂(SR)₁₅H. By combining the crystal structures and theoretical calculations, the focus was placed on the hydride-binding site, and a [Au-H] migration mechanism of this isomerization process is clearly shown. Furthermore, this [Au-H] migration mechanism is confirmed by the subsequent capture and structural determination of theoretically predicted intermediates. This work provides insight into the dynamic behavior of hydride ligands in nanoclusters and a strategy to study the evolution mechanism of nanoclusters by taking the hydride ligand as the breakthrough point.

Original language	English
Pages (from-to)	15859-15868
Number of pages	10
Journal	Journal of the American Chemical Society
Volume	145
Issue number	29
DOIs	https://doi.org/10.1021/jacs.3c02768
State	Published - Jul 26 2023

Funding

We acknowledge financial support of the following foundation. J.C. acknowledges the National Natural Science Foundation of China (22001002). S.Y. acknowledges the National Natural Science Foundation of China (22001003). Y.P. acknowledges the National Natural Science Foundation of China (91961121 and 21773201). M.Z. acknowledges the National Natural Science Foundation of China (21631001 and 21871001), the Ministry of Education, and the University Synergy Innovation Program of Anhui Province (GXXT-2020-053). The research used resources (TOPAZ beamline) at the ORNL Spallation Neutron Source, a Department of Energy (DOE) Office of Science User Facility. ORNL is managed by UT-Battelle LLC under DOE contract no. DE-AC05-00OR22725.

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title = "Mechanistic Study of the Hydride Migration-Induced Reversible Isomerization in Au22(SR)15H Isomers",

abstract = "Unraveling the evolution mechanism of metal nanoclusters is of great importance in understanding the formation and evolution of metallic condensed matters. In this work, the specific evolution process between a pair of gold nanocluster (Au NC) isomers is completely revealed by introducing hydride ligands to simplify the research system. A hydride-containing Au NC, Au22(SR)15H, was synthesized by kinetic control, and the positions of the hydrides were then confirmed by combining X-ray diffraction, neutron diffraction, and DFT calculations. Importantly, a reversible structural isomerization was found to occur on this Au22(SR)15H. By combining the crystal structures and theoretical calculations, the focus was placed on the hydride-binding site, and a [Au-H] migration mechanism of this isomerization process is clearly shown. Furthermore, this [Au-H] migration mechanism is confirmed by the subsequent capture and structural determination of theoretically predicted intermediates. This work provides insight into the dynamic behavior of hydride ligands in nanoclusters and a strategy to study the evolution mechanism of nanoclusters by taking the hydride ligand as the breakthrough point.",

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AU - Li, Qinzhen

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AU - Chai, Jinsong

AU - Wang, Xiaoping

AU - Pei, Yong

AU - Zhu, Manzhou

PY - 2023/7/26

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N2 - Unraveling the evolution mechanism of metal nanoclusters is of great importance in understanding the formation and evolution of metallic condensed matters. In this work, the specific evolution process between a pair of gold nanocluster (Au NC) isomers is completely revealed by introducing hydride ligands to simplify the research system. A hydride-containing Au NC, Au22(SR)15H, was synthesized by kinetic control, and the positions of the hydrides were then confirmed by combining X-ray diffraction, neutron diffraction, and DFT calculations. Importantly, a reversible structural isomerization was found to occur on this Au22(SR)15H. By combining the crystal structures and theoretical calculations, the focus was placed on the hydride-binding site, and a [Au-H] migration mechanism of this isomerization process is clearly shown. Furthermore, this [Au-H] migration mechanism is confirmed by the subsequent capture and structural determination of theoretically predicted intermediates. This work provides insight into the dynamic behavior of hydride ligands in nanoclusters and a strategy to study the evolution mechanism of nanoclusters by taking the hydride ligand as the breakthrough point.

AB - Unraveling the evolution mechanism of metal nanoclusters is of great importance in understanding the formation and evolution of metallic condensed matters. In this work, the specific evolution process between a pair of gold nanocluster (Au NC) isomers is completely revealed by introducing hydride ligands to simplify the research system. A hydride-containing Au NC, Au22(SR)15H, was synthesized by kinetic control, and the positions of the hydrides were then confirmed by combining X-ray diffraction, neutron diffraction, and DFT calculations. Importantly, a reversible structural isomerization was found to occur on this Au22(SR)15H. By combining the crystal structures and theoretical calculations, the focus was placed on the hydride-binding site, and a [Au-H] migration mechanism of this isomerization process is clearly shown. Furthermore, this [Au-H] migration mechanism is confirmed by the subsequent capture and structural determination of theoretically predicted intermediates. This work provides insight into the dynamic behavior of hydride ligands in nanoclusters and a strategy to study the evolution mechanism of nanoclusters by taking the hydride ligand as the breakthrough point.

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Mechanistic Study of the Hydride Migration-Induced Reversible Isomerization in Au₂₂(SR)₁₅H Isomers

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