0000000000494462
AUTHOR
Juanzhu Yan
showing 32 related works from this author
Embryonic Growth of Face-Center-Cubic Silver Nanoclusters Shaped in Nearly Perfect Half-Cubes and Cubes.
2016
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…
Atomically Precise, Thiolated Copper–Hydride Nanoclusters as Single-Site Hydrogenation Catalysts for Ketones in Mild Conditions
2019
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…
Plasmonic twinned silver nanoparticles with molecular precision
2016
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…
Thiol-Stabilized Atomically Precise, Superatomic Silver Nanoparticles for Catalyzing Cycloisomerization of Alkynyl Amines
2018
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…
Structural Evolution of Atomically Precise Thiolated Bimetallic [Au12+nCu32(SR)30+n]4– (n = 0, 2, 4, 6) Nanoclusters
2014
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
2015
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
2016
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…
Co-crystallization of atomically precise metal nanoparticles driven by magic atomic and electronic shells
2018
This paper reports co-crystallization of two atomically precise, different-size ligand-stabilized nanoclusters, a spherical (AuAg)267(SR)80 and a smaller trigonal-prismatic (AuAg)45(SR)27(PPh3)6 in 1:1 ratio, characterized fully by X-ray crystallographic analysis (SR = 2,4-SPhMe2). The larger cluster has a four concentric-shell icosahedral structure of Ag@M12@M42@M92@Ag120(SR)80 (M = Au or Ag) with the inner-core M147 icosahedron observed here for metal nanoparticles. The cluster has an open electron shell of 187 delocalized electrons, fully metallic, plasmonic behavior, and a zero HOMO-LUMO energy gap. The smaller cluster has an 18-electron shell closing, a notable HOMO-LUMO energy gap and…
From Symmetry Breaking to Unraveling the Origin of the Chirality of Ligated Au13 Cu2 Nanoclusters
2018
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…
From Symmetry Breaking to Unraveling the Origin of the Chirality of Ligated Au13Cu2 Nanoclusters
2018
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…
Asymmetric Synthesis of Chiral Bimetallic [Ag28Cu12(SR)24]4- Nanoclusters via Ion Pairing
2016
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
2014
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
2014
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
2017
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
2016
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
2017
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
2017
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
2017
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
2014
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 1814032: Experimental Crystal Structure Determination
2018
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
2019
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 1428884: Experimental Crystal Structure Determination
2015
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 1839942: Experimental Crystal Structure Determination
2018
Related Article: Juanzhu Yan, Sami Malola, Chengyi Hu, Jian Peng, Birger Dittrich, Boon K. Teo, Hannu Häkkinen, Lansun Zheng, Nanfeng Zheng|2018|Nat.Commun.|9|3357|doi:10.1038/s41467-018-05584-9
CCDC 1020497: Experimental Crystal Structure Determination
2014
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 1814033: Experimental Crystal Structure Determination
2018
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 1508753: Experimental Crystal Structure Determination
2016
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 1811378: Experimental Crystal Structure Determination
2018
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 1496142: Experimental Crystal Structure Determination
2016
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
2015
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
2014
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 1814031: Experimental Crystal Structure Determination
2018
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 1839941: Experimental Crystal Structure Determination
2018
Related Article: Juanzhu Yan, Sami Malola, Chengyi Hu, Jian Peng, Birger Dittrich, Boon K. Teo, Hannu Häkkinen, Lansun Zheng, Nanfeng Zheng|2018|Nat.Commun.|9|3357|doi:10.1038/s41467-018-05584-9