0000000000289779
AUTHOR
Guocheng Deng
showing 35 related works from this author
[Cu32(PET)24H8Cl2](PPh4)2: A Copper Hydride Nanocluster with a Bisquare Antiprismatic Core
2020
Atomically precise coinage metal (Au, Ag and Cu) nanoclusters (NCs) have been the subject of immense interest for their intriguing structural, photophysical and catalytic properties. However, the synthesis of Cu NCs is highly challenging because of low reduction potential and high reactivity of copper, demonstrating the need for new synthetic methods using appropriate ligand combinations. By designing a diamine-assisted synthetic strategy, here we report the synthesis and total structure characterization of a box-like dianionic Cu NC, [Cu32(PET)24H8Cl2](PPh4)2 co-protected by 2-phenylethanethiolate (PET), hydride and chloride ligands. Its crystal structure comprises a rare bisquare antipris…
Highly Robust but Surface-Active : An N-Heterocyclic Carbene-Stabilized Au25 Nanocluster
2019
Surface organic ligands play a critical role in stabilizing atomically precise metal nanoclusters in solutions. However, it is still challenging to prepare highly robust ligated metal nanoclusters that are surface-active for liquid-phase catalysis without any pre-treatment. Now, an N-heterocyclic carbene-stabilized Au25 nanocluster with high thermal and air stabilities is presented as a homogenous catalyst for cycloisomerization of alkynyl amines to indoles. The nanocluster, characterized as [Au25(iPr2-bimy)10Br7]2+ (iPr2-bimy=1,3-diisopropylbenzimidazolin-2-ylidene) (1), was synthesized by direct reduction of AuSMe2Cl and iPr2-bimyAuBr with NaBH4 in one pot. X-ray crystallization analysis …
Cd12Ag32(SePh)36 : Non-Noble Metal Doped Silver Nanoclusters
2019
While there are numerous recent reports on doping of a ligand-protected noble metal nanocluster (e.g., Au and Ag) with another noble metal, non-noble metal (e.g., Cd) doping remains challenging. Here, we design a phosphine-assisted synthetic strategy and synthesize a Cd doped Ag nanocluster, Cd12Ag32(SePh)36 (SePh: selenophenolate), which exhibits characteristic UV–vis absorption features and rare near-infrared (NIR) photoluminescence at ∼1020 nm. The X-ray single crystal structure reveals an asymmetric two-shell Ag4@Ag24 metal kernel protected by four nonplanar Cd3Ag(SePh)9 metal–ligand frameworks. Furthermore, the electronic structure analysis shows that the cluster is a 20-electron “supe…
Atomically Precise Alkynyl- and Halide-Protected AuAg Nanoclusters Au78Ag66(C≡CPh)48Cl8 and Au74Ag60(C≡CPh)40Br12: The Ligation Effects of Halides
2021
Reported herein are the synthesis and structures of two high-nuclearity AuAg nanoclusters, namely, [Au78Ag66(C≡CPh)48Cl8]q− and [Au74Ag60(C≡CPh)40Br12]2–. Both clusters possess a three-concentric-s...
Enhanced Surface Ligands Reactivity of Metal Clusters by Bulky Ligands for Controlling Optical and Chiral Properties.
2021
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
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…
Cd12Ag32(SePh)36: Non-Noble Metal Doped Silver Nanoclusters
2019
While there are numerous recent reports on doping of a ligand-protected noble metal nanocluster (e.g., Au and Ag) with another noble metal, non-noble metal (e.g., Cd) doping remains challenging. Here, we design a phosphine-assisted synthetic strategy and synthesize a Cd doped Ag nanocluster, Cd12Ag32(SePh)36 (SePh: selenophenolate), which exhibits characteristic UV–vis absorption features and rare near-infrared (NIR) photoluminescence at ∼1020 nm. The X-ray single crystal structure reveals an asymmetric two-shell Ag4@Ag24 metal kernel protected by four nonplanar Cd3Ag(SePh)9 metal–ligand frameworks. Furthermore, the electronic structure analysis shows that the cluster is a 20-electron “supe…
[Cu32(PET)24H8Cl2](PPh4)2: A Copper Hydride Nanocluster with a Bisquare Antiprismatic Core
2020
Atomically precise coinage metal (Au, Ag, and Cu) nanoclusters (NCs) have been the subject of immense interest for their intriguing structural, photophysical, and catalytic properties. However, the synthesis of Cu NCs is highly challenging because of low reduction potential and high reactivity of copper, demonstrating the need for new synthetic methods using appropriate ligand combinations. By designing a diamine-assisted synthetic strategy, here we report the synthesis and total structure characterization of a box-like dianionic Cu NC [Cu32(PET)24H8Cl2](PPh4)2 coprotected by 2-phenylethanethiolate (PET), hydride, and chloride ligands. Its crystal structure comprises a rare bisquare antipri…
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…
Highly Robust but Surface-Active: N-Heterocyclic Carbene-Stabilized Au25 Nanocluster as a Homogeneous Catalyst
2019
<div> <div> <div> <p>Surface organic ligands play a critical role in stabilizing atomically precise metal nanoclusters in solutions. However, it is still challenging to prepare highly robust ligated metal nanoclusters that are surface-active for liquid-phase catalysis without any pre-treatment. Herein, we report a novel N-heterocyclic carbine-stabilized Au25 nanocluster with high thermal and air stabilities as a homogenous catalyst for cycloisomerization of alkynyl amines to indoles. The nanocluster, characterized as [Au25(iPr2-bimy)10Br7]2+ (iPr2-bimy=diisopropyl-benzilidazolium) (1), was synthesized by direct reduction of AuSMe2Cl and iPr2- bimyAuBr with NaBH4 in o…
Highly Robust but Surface‐Active: An N‐Heterocyclic Carbene‐Stabilized Au 25 Nanocluster
2019
Surface organic ligands play a critical role in stabilizing atomically precise metal nanoclusters in solutions. However, it is still challenging to prepare highly robust ligated metal nanoclusters that are surface-active for liquid-phase catalysis without any pre-treatment. Now, an N-heterocyclic carbene-stabilized Au25 nanocluster with high thermal and air stabilities is presented as a homogenous catalyst for cycloisomerization of alkynyl amines to indoles. The nanocluster, characterized as [Au25 (i Pr2 -bimy)10 Br7 ]2+ (i Pr2 -bimy=1,3-diisopropylbenzimidazolin-2-ylidene) (1), was synthesized by direct reduction of AuSMe2 Cl and i Pr2 -bimyAuBr with NaBH4 in one pot. X-ray crystallization…
[Pt2Cu34(PET)22Cl4]2–: An Atomically Precise, 10-Electron PtCu Bimetal Nanocluster with a Direct Pt–Pt Bond
2021
Heteroatom-doped metal nanoclusters (NCs) are highly desirable to gain fundamental insights into the effect of doping on the electronic structure and catalytic properties. Unfortunately, their controlled synthesis is highly challenging when the metal atomic sizes are largely different (e.g., Cu and Pt). Here, we design a metal-exchange strategy that enables simultaneous doping and resizing of NCs. Specifically, [Pt2Cu34(PET)22Cl4]2- NC, the first example of a Pt-doped Cu NC, is synthesized by utilizing the unique reactivity of [Cu32(PET)24Cl2H8]2- NC with Pt4+ ions. The single-crystal X-ray structure reveals that two directly bonded Pt atoms occupy the two centers of an unusually interpenet…
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…
Ag44(EBT)26(TPP)4Nanoclusters With Tailored Molecular and Electronic Structure
2021
Although atomically precise metalloid nanoclusters (NCs) of identical size with distinctly different molecular structures are highly desirable to understand the structural effects on the optical and photophysical properties, their synthesis remains highly challenging. Herein, we employed phosphine and thiol capping ligands featuring appropriate steric effects and synthesized a charge-neutral Ag NC with the formula Ag44 (EBT)26 (TPP)4 (EBT: 2-ethylbenzenethiolate; TPP: triphenylphosphine). The single-crystal X-ray structure reveals that this NC has a hollow metal core of Ag12 @Ag20 and a metal-ligand shell of Ag12 (EBT)26 (TPP)4 . The presence of mixed ligands and long V-shaped metal-ligand …
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…
Ag44(EBT)26(TPP)4 Nanoclusters with Tailored Molecular and Electronic Structure
2021
Although atomically precise metalloid nanoclusters (NCs) of identical size with distinctly different molecular structures are highly desirable to understand the structural effects on the intriguing optical and photophysical properties, their synthesis remains highly challenging. Herein, we employed phosphine and thiol capping ligands featuring appropriate steric effects and synthesized a charge‐neutral Ag NC with the formula, Ag 44 (EBT) 26 (TPP) 4 (EBT: 2‐ethylbenzenethiolate; TPP: triphenylphosphine). The single‐crystal X‐ray structure reveals that this NC has a hollow metal core of Ag 12 @Ag 20 and a metal‐ligand shell of Ag 12 (EBT) 26 (TPP) 4 . The presence of mixed ligands and long V‐…
Alkynyl‐Protected Chiral Bimetallic Ag22Cu7 Superatom with Multiple Chirality Origins
2023
Understanding the origin of chirality in the nanostructured materials is essential for chiroptical and catalytic applications. Here we report a chiral AgCu superatomic cluster, [Ag22Cu7(C≡CR)16(PPh3)5Cl6](PPh4), Ag22Cu7, protected by an achiral alkynyl ligand (HC≡CR: 3,5-bis(trifluoromethyl)phenylacetylene). Its crystal structure comprises a rare interpenetrating biicosahedral Ag17Cu2 core, which is stabilized by four different types of motifs: one Cu(C≡CR)2, four -C≡CR, two chlorides and one helical Ag5Cu4(C≡CR)10(PPh3)5Cl4. Structural analysis reveals that Ag22Cu7 exhibits multiple chirality origins, including the metal core, the metal-ligand interface and the ligand layer. Furthermore, t…
CCDC 2054076: Experimental Crystal Structure Determination
2021
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 2044601: Experimental Crystal Structure Determination
2021
Related Article: Xiting Yuan, Sami Malola, Guocheng Deng, Fengjiao Chen, Hannu Häkkinen, Boon K. Teo, Lansun Zheng, Nanfeng Zheng|2021|Inorg.Chem.|60|3529|doi:10.1021/acs.inorgchem.0c03462
CCDC 2054077: Experimental Crystal Structure Determination
2021
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 2044592: Experimental Crystal Structure Determination
2021
Related Article: Xiting Yuan, Sami Malola, Guocheng Deng, Fengjiao Chen, Hannu Häkkinen, Boon K. Teo, Lansun Zheng, Nanfeng Zheng|2021|Inorg.Chem.|60|3529|doi:10.1021/acs.inorgchem.0c03462
CCDC 1814032: Experimental Crystal Structure Determination
2018
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CCDC 1851619: Experimental Crystal Structure Determination
2019
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CCDC 1918141: Experimental Crystal Structure Determination
2019
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CCDC 1814033: Experimental Crystal Structure Determination
2018
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CCDC 2054074: Experimental Crystal Structure Determination
2021
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
2021
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CCDC 2054075: Experimental Crystal Structure Determination
2021
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CCDC 2021376: Experimental Crystal Structure Determination
2020
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CCDC 1811378: Experimental Crystal Structure Determination
2018
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CCDC 2071611: Experimental Crystal Structure Determination
2021
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CCDC 2054078: Experimental Crystal Structure Determination
2021
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CCDC 1814031: Experimental Crystal Structure Determination
2018
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CCDC 1916156: Experimental Crystal Structure Determination
2019
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CCDC 2032634: Experimental Crystal Structure Determination
2021
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