0000000001300227
AUTHOR
Huayan Yang
Embryonic Growth of Face-Center-Cubic Silver Nanoclusters Shaped in Nearly Perfect Half-Cubes and Cubes.
Demonstrated herein are the preparation and crystallographic characterization of the family of fcc silver nanoclusters from Nichol’s cube to Rubik’s cube and beyond via ligand-control (thiolates and phosphines in this case). The basic building block is our previously reported fcc cluster [Ag14(SPhF2)12(PPh3)8] (1). The metal frameworks of [Ag38(SPhF2)26(PR′3)8] (22) and [Ag63(SPhF2)36(PR′3)8]+ (23), where HSPhF2 = 3,4-difluorothiophenol and R′ = alkyl/aryl, are composed of 2 × 2 = 4 and 2 × 2 × 2 = 8 metal cubes of 1, respectively. All serial clusters share similar surface structural features. The thiolate ligands cap the six faces and the 12 edges of the cube (or half cube) while the phosp…
All-thiol-stabilized Ag44 and Au12Ag32 nanoparticles with single-crystal structures
Noble metal nanoparticles stabilized by organic ligands are important for applications in assembly, site-specific bioconjugate labelling and sensing, drug delivery and medical therapy, molecular recognition and molecular electronics, and catalysis. Here we report crystal structures and theoretical analysis of three Ag44(SR)30 and three Au12Ag32(SR)30 intermetallic nanoclusters stabilized with fluorinated arylthiols (SR=SPhF, SPhF2 or SPhCF3). The nanocluster forms a Keplerate solid of concentric icosahedral and dodecahedral atom shells, protected by six Ag2(SR)5 units. Positive counterions in the crystal indicate a high negative charge of 4(-) per nanoparticle, and density functional theory…
Ligand-Stabilized Au13Cux (x = 2, 4, 8) Bimetallic Nanoclusters: Ligand Engineering to Control the Exposure of Metal Sites
Three novel bimetallic Au-Cu nanoclusters stabilized by a mixed layer of thiolate and phosphine ligands bearing pyridyl groups are synthesized and fully characterized by X-ray single crystal analysis and density functional theory computations. The three clusters have an icosahedral Au13 core face-capped by two, four, and eight Cu atoms, respectively. All face-capping Cu atoms in the clusters are triply coordinated by thiolate or pyridyl groups. The surface ligands control the exposure of Au sites in the clusters. In the case of the Au13Cu8 cluster, the presence of 12 2-pyridylthiolate ligands still leaves open space for catalysis. All the 3 clusters are 8-electron superatoms displaying opti…
Plasmonic twinned silver nanoparticles with molecular precision
Determining the structures of nanoparticles at atomic resolution is vital to understand their structure–property correlations. Large metal nanoparticles with core diameter beyond 2 nm have, to date, eluded characterization by single-crystal X-ray analysis. Here we report the chemical syntheses and structures of two giant thiolated Ag nanoparticles containing 136 and 374 Ag atoms (that is, up to 3 nm core diameter). As the largest thiolated metal nanoparticles crystallographically determined so far, these Ag nanoparticles enter the truly metallic regime with the emergence of surface plasmon resonance. As miniatures of fivefold twinned nanostructures, these structures demonstrate a subtle dis…
Asymmetric Synthesis of Chiral Bimetallic [Ag28Cu12(SR)24]4- Nanoclusters via Ion Pairing
In this work, a facile ion-pairing strategy for asymmetric synthesis of optically active negatively charged chiral metal nanoparticles using chiral ammonium cations is demonstrated. A new thiolated chiral three-concentric-shell cluster, [Ag28Cu12(SR)24] 4- was first synthesized as a racemic mixture and characterized by single-crystal X-ray structure determination. Mass spectrometric measurements revealed relatively strong ion-pairing interactions between the anionic nanocluster and ammonium cations. Inspired by this observation, the as-prepared racemic mixture was separated into enantiomers by employing chiral quaternary ammonium salts as chiral resolution agents. Subsequently, direct asymm…
Structural Evolution of Atomically Precise Thiolated Bimetallic [Au12+nCu32(SR)30+n]4– (n = 0, 2, 4, 6) Nanoclusters
A series of all-thiol stabilized bimetallic Au-Cu nanoclusters, [Au(12+n)Cu32(SR)(30+n)](4-) (n = 0, 2, 4, 6 and SR = SPhCF3), are successfully synthesized and characterized by X-ray single-crystal analysis and density functional theory (DFT) calculations. Each cluster consists of a Keplerate two-shell Au12@Cu20 core protected by (6 - n) units of Cu2(SR)5 and n units of Cu2Au(SR)6 (n = 0, 2, 4, 6) motifs on its surface. The size and structural evolution of the clusters is atomically controlled by the Au precursors and countercations used in the syntheses. The clusters exhibit similar optical absorption properties that are not dependent on the number of surface Cu2Au(SR)6 units. Although DFT…
Total Structure and Electronic Structure Analysis of Doped Thiolated Silver [MAg24(SR)18]2– (M = Pd, Pt) Clusters
With the incorporation of Pd or Pt atoms, thiolated Ag-rich 25-metal-atom nanoclusters were successfully prepared and structurally characterized for the first time. With a composition of [PdAg24(SR)18](2-) or [PtAg24(SR)18](2-), the obtained 25-metal-atom nanoclusters have a metal framework structure similar to that of widely investigated Au25(SR)18. In both clusters, a M@Ag12 (M = Pd, Pt) core is capped by six distorted dimeric -RS-Ag-SR-Ag-SR- units. However, the silver-thiolate overlayer gives rise to a geometric chirality at variance to Au25(SR)18. The effect of doping on the electronic structure was studied through measured optical absorption spectra and ab initio analysis. This work d…
Asymmetric Synthesis of Chiral Bimetallic [Ag28Cu12(SR)24]4– Nanoclusters via Ion Pairing
In this work, a facile ion-pairing strategy for asymmetric synthesis of optically active negatively charged chiral metal nanoparticles using chiral ammonium cations is demonstrated. A new thiolated chiral three-concentric-shell cluster, [Ag28Cu12(SR)24]4–, was first synthesized as a racemic mixture and characterized by single-crystal X-ray structure determination. Mass spectrometric measurements revealed relatively strong ion-pairing interactions between the anionic nanocluster and ammonium cations. Inspired by this observation, the as-prepared racemic mixture was separated into enantiomers by employing chiral quaternary ammonium salts as chiral resolution agents. Subsequently, direct asymm…
CCDC 1020498: Experimental Crystal Structure Determination
Related Article: Huayan Yang , Yu Wang , Juanzhu Yan , Xi Chen , Xin Zhang , Hannu Häkkinen , and Nanfeng Zheng|2014|J.Am.Chem.Soc.|136|7197|doi:10.1021/ja501811j
CCDC 1020499: Experimental Crystal Structure Determination
Related Article: Huayan Yang , Yu Wang , Juanzhu Yan , Xi Chen , Xin Zhang , Hannu Häkkinen , and Nanfeng Zheng|2014|J.Am.Chem.Soc.|136|7197|doi:10.1021/ja501811j
CCDC 1530605: Experimental Crystal Structure Determination
Related Article: Huayan Yang, Juanzhu Yan, Yu Wang, Haifeng Su, Lars Gell, Xiaojing Zhao, Chaofa Xu, Boon K. Teo, Hannu Häkkinen , and Nanfeng Zheng|2017|J.Am.Chem.Soc.|139|31|doi:10.1021/jacs.6b10053
CCDC 1496141: Experimental Crystal Structure Determination
Related Article: Huayan Yang, Yu Wang, Xi Chen, Xiaojing Zhao, Lin Gu, Huaqi Huang, Juanzhu Yan, Chaofa Xu, Gang Li, Junchao Wu, Alison J. Edwards, Birger Dittrich, Zichao Tang, Dongdong Wang, Lauri Lehtovaara, Hannu Häkkinen, Nanfeng Zheng|2016|Nat.Commun.|7|12809|doi:10.1038/ncomms12809
CCDC 1530607: Experimental Crystal Structure Determination
Related Article: Huayan Yang, Juanzhu Yan, Yu Wang, Haifeng Su, Lars Gell, Xiaojing Zhao, Chaofa Xu, Boon K. Teo, Hannu Häkkinen , and Nanfeng Zheng|2017|J.Am.Chem.Soc.|139|31|doi:10.1021/jacs.6b10053
CCDC 1530606: Experimental Crystal Structure Determination
Related Article: Huayan Yang, Juanzhu Yan, Yu Wang, Haifeng Su, Lars Gell, Xiaojing Zhao, Chaofa Xu, Boon K. Teo, Hannu Häkkinen , and Nanfeng Zheng|2017|J.Am.Chem.Soc.|139|31|doi:10.1021/jacs.6b10053
CCDC 1530604: Experimental Crystal Structure Determination
Related Article: Huayan Yang, Juanzhu Yan, Yu Wang, Haifeng Su, Lars Gell, Xiaojing Zhao, Chaofa Xu, Boon K. Teo, Hannu Häkkinen , and Nanfeng Zheng|2017|J.Am.Chem.Soc.|139|31|doi:10.1021/jacs.6b10053
CCDC 1020496: Experimental Crystal Structure Determination
Related Article: Huayan Yang , Yu Wang , Juanzhu Yan , Xi Chen , Xin Zhang , Hannu Häkkinen , and Nanfeng Zheng|2014|J.Am.Chem.Soc.|136|7197|doi:10.1021/ja501811j
CCDC 953878: Experimental Crystal Structure Determination
Related Article: Huayan Yang, Yu Wang, Huaqi Huang, Lars Gell, Lauri Lehtovaara, Sami Malola, Hannu Hakkinen, Nanfeng Zheng|2013|Nat.Commun.|4|2422|doi:10.1038/ncomms3422
CCDC 1428884: Experimental Crystal Structure Determination
Related Article: Juanzhu Yan, Haifeng Su, Huayan Yang, Sami Malola, Shuichao Lin, Hannu Häkkinen, and Nanfeng Zheng|2015|J.Am.Chem.Soc.|137|11880|doi:10.1021/jacs.5b07186
CCDC 953880: Experimental Crystal Structure Determination
Related Article: Huayan Yang, Yu Wang, Huaqi Huang, Lars Gell, Lauri Lehtovaara, Sami Malola, Hannu Hakkinen, Nanfeng Zheng|2013|Nat.Commun.|4|2422|doi:10.1038/ncomms3422
CCDC 953881: Experimental Crystal Structure Determination
Related Article: Huayan Yang, Yu Wang, Huaqi Huang, Lars Gell, Lauri Lehtovaara, Sami Malola, Hannu Hakkinen, Nanfeng Zheng|2013|Nat.Commun.|4|2422|doi:10.1038/ncomms3422
CCDC 1020497: Experimental Crystal Structure Determination
Related Article: Huayan Yang , Yu Wang , Juanzhu Yan , Xi Chen , Xin Zhang , Hannu Häkkinen , and Nanfeng Zheng|2014|J.Am.Chem.Soc.|136|7197|doi:10.1021/ja501811j
CCDC 954905: Experimental Crystal Structure Determination
Related Article: Huayan Yang , Yu Wang , Jing Lei , Lei Shi , Xiaohu Wu , Ville Mäkinen , Shuichao Lin , Zichao Tang , Jian He , Hannu Häkkinen , Lansun Zheng , and Nanfeng Zheng|2013|J.Am.Chem.Soc.|135|9568|doi:10.1021/ja402249s
CCDC 1508753: Experimental Crystal Structure Determination
Related Article: Juanzhu Yan, Haifeng Su, Huayan Yang, Chengyi Hu, Sami Malola, Shuichao Lin, Boon K. Teo, Hannu Häkkinen, and Nanfeng Zheng|2016|J.Am.Chem.Soc.|138|12751|doi:10.1021/jacs.6b08100
CCDC 954903: Experimental Crystal Structure Determination
Related Article: Huayan Yang , Yu Wang , Jing Lei , Lei Shi , Xiaohu Wu , Ville Mäkinen , Shuichao Lin , Zichao Tang , Jian He , Hannu Häkkinen , Lansun Zheng , and Nanfeng Zheng|2013|J.Am.Chem.Soc.|135|9568|doi:10.1021/ja402249s
CCDC 954904: Experimental Crystal Structure Determination
Related Article: Huayan Yang , Yu Wang , Jing Lei , Lei Shi , Xiaohu Wu , Ville Mäkinen , Shuichao Lin , Zichao Tang , Jian He , Hannu Häkkinen , Lansun Zheng , and Nanfeng Zheng|2013|J.Am.Chem.Soc.|135|9568|doi:10.1021/ja402249s
CCDC 953883: Experimental Crystal Structure Determination
Related Article: Huayan Yang, Yu Wang, Huaqi Huang, Lars Gell, Lauri Lehtovaara, Sami Malola, Hannu Hakkinen, Nanfeng Zheng|2013|Nat.Commun.|4|2422|doi:10.1038/ncomms3422
CCDC 953879: Experimental Crystal Structure Determination
Related Article: Huayan Yang, Yu Wang, Huaqi Huang, Lars Gell, Lauri Lehtovaara, Sami Malola, Hannu Hakkinen, Nanfeng Zheng|2013|Nat.Commun.|4|2422|doi:10.1038/ncomms3422
CCDC 953882: Experimental Crystal Structure Determination
Related Article: Huayan Yang, Yu Wang, Huaqi Huang, Lars Gell, Lauri Lehtovaara, Sami Malola, Hannu Hakkinen, Nanfeng Zheng|2013|Nat.Commun.|4|2422|doi:10.1038/ncomms3422
CCDC 1496142: Experimental Crystal Structure Determination
Related Article: Huayan Yang, Yu Wang, Xi Chen, Xiaojing Zhao, Lin Gu, Huaqi Huang, Juanzhu Yan, Chaofa Xu, Gang Li, Junchao Wu, Alison J. Edwards, Birger Dittrich, Zichao Tang, Dongdong Wang, Lauri Lehtovaara, Hannu Häkkinen, Nanfeng Zheng|2016|Nat.Commun.|7|12809|doi:10.1038/ncomms12809
CCDC 1428883: Experimental Crystal Structure Determination
Related Article: Juanzhu Yan, Haifeng Su, Huayan Yang, Sami Malola, Shuichao Lin, Hannu Häkkinen, and Nanfeng Zheng|2015|J.Am.Chem.Soc.|137|11880|doi:10.1021/jacs.5b07186
CCDC 1020495: Experimental Crystal Structure Determination
Related Article: Huayan Yang , Yu Wang , Juanzhu Yan , Xi Chen , Xin Zhang , Hannu Häkkinen , and Nanfeng Zheng|2014|J.Am.Chem.Soc.|136|7197|doi:10.1021/ja501811j