0000000000211565
AUTHOR
Peng Yuan
Bulky Surface Ligands Promote Surface Reactivities of [Ag141X12(S-Adm)40]3+ (X=Cl, Br, I) Nanoclusters: Models for Multiple-Twinned Nanoparticles
Surface ligands play important roles in controlling the size and shape of metal nanoparticles and their surface properties. In this work, we demonstrate that the use of bulky thiolate ligands, along with halides, as the surface capping agent promotes the formation of plasmonic multiple-twinned Ag nanoparticles with high surface reactivities. The title nanocluster [Ag141X12(S-Adm)40]3+ (where X = Cl, Br, I; S-Adm = 1-adamantanethiolate) has a multiple-shell structure with an Ag71 core protected by a shell of Ag70X12(S-Adm)40. The Ag71 core can be considered as 20 frequency-two Ag10 tetrahedra fused together with a dislocation that resembles multiple-twinning in nanoparticles. The nanocluster…
From Symmetry Breaking to Unraveling the Origin of the Chirality of Ligated Au13Cu2 Nanoclusters
A general method, using mixed ligands (here diphosphines and thiolates) is devised to turn an achiral metal cluster, Au13Cu2, into an enantiomeric pair by breaking (lowering) the overall molecular symmetry with the ligands. Using an achiral diphosphine, a racemic [Au13Cu2(DPPP)3(SPy)6]+ was prepared which crystallizes in centrosymmetric space groups. Using chiral diphosphines, enantioselective synthesis of an optically pure, enantiomeric pair of [Au13Cu2((2r,4r)/(2s,4s)‐BDPP)3(SPy)6]+ was achieved in one pot. Their circular dichroism (CD) spectra give perfect mirror images in the range of 250–500 nm with maximum anisotropy factors of 1.2×10−3. DFT calculations provided good correlations wit…
Solubility-Driven Isolation of a Metastable Nonagold Cluster with Body-Centered Cubic Structure.
The conventional synthetic methodology of atomically precise gold nanoclusters using reduction in solutions offers only thermodynamically most stable nanoclusters. We report herein a solubility‐driven isolation strategy to access the synthesis of a metastable gold cluster. The cluster, with the composition of [Au 9 (PPh 3 ) 8 ] + ( 1 ), displays an unusual, nearly perfect body‐centered‐cubic (bcc) structure. As revealed by ESI‐MS and UV/Vis measurement, the cluster is metastable in solution and converts to the well‐known [Au 11 (PPh 3 ) 8 Cl 2 ] + ( 2 ) within just 90 min. DFT calculations revealed that while both 1 and 2 are eight‐electron superatoms, there is a driving force to convert 1 …
Solvent-mediated assembly of atom-precise gold–silver nanoclusters to semiconducting one-dimensional materials
Bottom-up design of functional device components based on nanometer-sized building blocks relies on accurate control of their self-assembly behavior. Atom-precise metal nanoclusters are well-characterizable building blocks for designing tunable nanomaterials, but it has been challenging to achieve directed assembly to macroscopic functional cluster-based materials with highly anisotropic properties. Here, we discover a solvent-mediated assembly of 34-atom intermetallic gold–silver clusters protected by 20 1-ethynyladamantanes into 1D polymers with Ag–Au–Ag bonds between neighboring clusters as shown directly by the atomic structure from single-crystal X-ray diffraction analysis. Density fun…
Enhanced Surface Ligands Reactivity of Metal Clusters by Bulky Ligands for Controlling Optical and Chiral Properties.
Surface ligands play critical roles in determining the surface properties of metal clusters. However, modulating the properties and controlling the surface structure of clusters through surface‐capping agent displacement remain a challenge. In this work, a silver cluster, [Ag 14 (SPh(CF 3 ) 2 ) 12 (PPh 3 ) 4 (DMF) 4 ] ( Ag 14 ‐DMF , where HSPh(CF 3 ) 2 is 3,5‐bis(trifluoromethyl)benzenethiol, PPh 3 is triphenylphosphine and DMF is N,N‐Dimethylformamide), with weakly coordinated DMF ligands on the surface silver sites, was synthesized by using a mixed ligands strategy (bulky thiolates, phosphines and small solvents). The as‐prepared Ag 14 ‐DMF is a racemic mixture of chiral molecules. Owing …
Atomically Precise, Thiolated Copper–Hydride Nanoclusters as Single-Site Hydrogenation Catalysts for Ketones in Mild Conditions
Copper-hydrides are known catalysts for several technologically important reactions such as hydrogenation of CO, hydroamination of alkenes and alkynes, and chemoselective hydrogenation of unsaturated ketones to unsaturated alcohols. Stabilizing copper-based particles by ligand chemistry to nanometer scale is an appealing route to make active catalysts with optimized material economy; however, it has been long believed that the ligand-metal interface, particularly if sulfur-containing thiols are used as stabilizing agent, may poison the catalyst. We report here a discovery of an ambient-stable thiolate-protected copper-hydride nanocluster [Cu25H10(SPhCl2)18]3- that readily catalyzes hydrogen…
Bulky Surface Ligands Promote Surface Reactivities of [Ag141X12(S-Adm)40]3+ (X = Cl, Br, I) Nanoclusters: Models for Multiple-Twinned Nanoparticles
Surface ligands play important roles in controlling the size and shape of metal nanoparticles and their surface properties. In this work, we demonstrate that the use of bulky thiolate ligands, along with halides, as the surface capping agent promotes the formation of plasmonic multiple-twinned Ag nanoparticles with high surface reactivities. The title nanocluster [Ag141X12(S-Adm)40]3+ (where X = Cl, Br, I; S-Adm = 1-adamantanethiolate) has a multiple-shell structure with an Ag71 core protected by a shell of Ag70X12(S-Adm)40. The Ag71 core can be considered as 20 frequency-two Ag10 tetrahedra fused together with a dislocation that resembles multiple-twinning in nanoparticles. The nanocluster…
Thiol-Stabilized Atomically Precise, Superatomic Silver Nanoparticles for Catalyzing Cycloisomerization of Alkynyl Amines
Abstract Both the electronic and surface structures of metal nanomaterials play critical roles in determining their chemical properties. However, the non-molecular nature of conventional nanoparticles makes it extremely challenging to understand the molecular mechanism behind many of their unique electronic and surface properties. In this work, we report the synthesis, molecular and electronic structures of an atomically precise nanoparticle, [Ag206L72]q (L = thiolate, halide; q = charge). With a four-shell Ag7@Ag32@Ag77@Ag90 Ino-decahedral structure having a nearly perfect D5h symmetry, the metal core of the nanoparticle is co-stabilized by 68 thiolate and 4 halide ligands. Both electroche…
From Symmetry Breaking to Unraveling the Origin of the Chirality of Ligated Au13 Cu2 Nanoclusters
A general method, using mixed ligands (here diphosphines and thiolates) is devised to turn an achiral metal cluster, Au13 Cu2 , into an enantiomeric pair by breaking (lowering) the overall molecular symmetry with the ligands. Using an achiral diphosphine, a racemic [Au13 Cu2 (DPPP)3 (SPy)6 ]+ was prepared which crystallizes in centrosymmetric space groups. Using chiral diphosphines, enantioselective synthesis of an optically pure, enantiomeric pair of [Au13 Cu2 ((2r,4r)/(2s,4s)-BDPP)3 (SPy)6 ]+ was achieved in one pot. Their circular dichroism (CD) spectra give perfect mirror images in the range of 250-500 nm with maximum anisotropy factors of 1.2×10-3 . DFT calculations provided good corre…
CCDC 2054076: Experimental Crystal Structure Determination
Related Article: Guocheng Deng, Sami Malola, Peng Yuan, Xianhu Liu, Boon K. Teo, Hannu Häkkinen, Nanfeng Zheng|2021|Angew.Chem.,Int.Ed.|60|12897|doi:10.1002/anie.202101141
CCDC 2054077: Experimental Crystal Structure Determination
Related Article: Guocheng Deng, Sami Malola, Peng Yuan, Xianhu Liu, Boon K. Teo, Hannu Häkkinen, Nanfeng Zheng|2021|Angew.Chem.,Int.Ed.|60|12897|doi:10.1002/anie.202101141
CCDC 1543483: Experimental Crystal Structure Determination
Related Article: Liting Ren, Peng Yuan, Haifeng Su, Sami Malola, Shuichao Lin, Zichao Tang, Boon K. Teo, Hannu Häkkinen , Lansun Zheng, and Nanfeng Zheng|2017|J.Am.Chem.Soc.|139|13288|doi:10.1021/jacs.7b07926
CCDC 1814032: Experimental Crystal Structure Determination
Related Article: Guocheng Deng, Sami Malola, Juanzhu Yan, Yingzi Han, Peng Yuan, Chaowei Zhao, Xiting Yuan, Shuichao Lin, Zichao Tang, Boon K. Teo, Hannu Häkkinen, Nanfeng Zheng|2018|Angew.Chem.,Int.Ed.|57|3421|doi:10.1002/anie.201800327
CCDC 1851619: Experimental Crystal Structure Determination
Related Article: Cunfa Sun, Nisha Mammen, Sami Kaappa, Peng Yuan, Guocheng Deng, Chaowei Zhao, Juanzhu Yan, Sami Malola, Karoliina Honkala, Hannu Häkkinen, Boon K. Teo, Nanfeng Zheng|2019|ACS Nano|13|5975|doi:10.1021/acsnano.9b02052
CCDC 1962411: Experimental Crystal Structure Determination
Related Article: Peng Yuan, Ruihua Zhang, Elli Selenius, Pengpeng Ruan, Yangrong Yao, Yang Zhou, Sami Malola, Hannu Häkkinen, Boon K. Teo, Yang Cao, Nanfeng Zheng|2020|Nat.Commun.|11|2229|doi:10.1038/s41467-020-16062-6
CCDC 1962412: Experimental Crystal Structure Determination
Related Article: Peng Yuan, Ruihua Zhang, Elli Selenius, Pengpeng Ruan, Yangrong Yao, Yang Zhou, Sami Malola, Hannu Häkkinen, Boon K. Teo, Yang Cao, Nanfeng Zheng|2020|Nat.Commun.|11|2229|doi:10.1038/s41467-020-16062-6
CCDC 1814033: Experimental Crystal Structure Determination
Related Article: Guocheng Deng, Sami Malola, Juanzhu Yan, Yingzi Han, Peng Yuan, Chaowei Zhao, Xiting Yuan, Shuichao Lin, Zichao Tang, Boon K. Teo, Hannu Häkkinen, Nanfeng Zheng|2018|Angew.Chem.,Int.Ed.|57|3421|doi:10.1002/anie.201800327
CCDC 2054074: Experimental Crystal Structure Determination
Related Article: Guocheng Deng, Sami Malola, Peng Yuan, Xianhu Liu, Boon K. Teo, Hannu Häkkinen, Nanfeng Zheng|2021|Angew.Chem.,Int.Ed.|60|12897|doi:10.1002/anie.202101141
CCDC 2054073: Experimental Crystal Structure Determination
Related Article: Guocheng Deng, Sami Malola, Peng Yuan, Xianhu Liu, Boon K. Teo, Hannu Häkkinen, Nanfeng Zheng|2021|Angew.Chem.,Int.Ed.|60|12897|doi:10.1002/anie.202101141
CCDC 2054075: Experimental Crystal Structure Determination
Related Article: Guocheng Deng, Sami Malola, Peng Yuan, Xianhu Liu, Boon K. Teo, Hannu Häkkinen, Nanfeng Zheng|2021|Angew.Chem.,Int.Ed.|60|12897|doi:10.1002/anie.202101141
CCDC 1811378: Experimental Crystal Structure Determination
Related Article: Juanzhu Yan, Jun Zhang, Xumao Chen, Sami Malola, Bo Zhou, Elli Selenius, Xiaomin Zhang, Peng Yuan, Guocheng Deng, Kunlong Liu, Haifeng Su, Boon K. Teo, Hannu Häkkinen, Lansun Zheng, Nanfeng Zheng|2018|National Science Review|5|694|doi:10.1093/nsr/nwy034
CCDC 2054078: Experimental Crystal Structure Determination
Related Article: Guocheng Deng, Sami Malola, Peng Yuan, Xianhu Liu, Boon K. Teo, Hannu Häkkinen, Nanfeng Zheng|2021|Angew.Chem.,Int.Ed.|60|12897|doi:10.1002/anie.202101141
CCDC 1967410: Experimental Crystal Structure Determination
Related Article: Hui Shen, Elli Selenius, Pengpeng Ruan, Xihua Li, Peng Yuan, Omar Lopez-Estrada, Sami Malola, Shuichao Lin, Boon K. Teo, Hannu Häkkinen, Nanfeng Zheng|2020|Chem.-Eur.J.|26|8465|doi:10.1002/chem.202001753
CCDC 1543485: Experimental Crystal Structure Determination
Related Article: Liting Ren, Peng Yuan, Haifeng Su, Sami Malola, Shuichao Lin, Zichao Tang, Boon K. Teo, Hannu Häkkinen , Lansun Zheng, and Nanfeng Zheng|2017|J.Am.Chem.Soc.|139|13288|doi:10.1021/jacs.7b07926
CCDC 1814031: Experimental Crystal Structure Determination
Related Article: Guocheng Deng, Sami Malola, Juanzhu Yan, Yingzi Han, Peng Yuan, Chaowei Zhao, Xiting Yuan, Shuichao Lin, Zichao Tang, Boon K. Teo, Hannu Häkkinen, Nanfeng Zheng|2018|Angew.Chem.,Int.Ed.|57|3421|doi:10.1002/anie.201800327