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RESEARCH PAPER · Journal of the American Chemical Society · 2019

Efficient and Selective Conversion of Phosphine-Protected (MAu8)2+ (M = Pd, Pt) Superatoms to Thiolate-Protected (MAu12)6+ or Alkynyl-Protected (MAu12)4+ Superatoms via Hydride Doping

Shinjiro Takano, Shun Ito, Tatsuya Tsukuda

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Efficient and Selective Conversion of Phosphine-Protected (MAu8)2+ (M = Pd, Pt) Superatoms to Thiolate-Protected (MAu12)6+ or Alkynyl-Protected (MAu12)4+ Superatoms via Hydride DopingOriginalAlkynyl-Protected Au22(C≡CR)18 Clusters Featuring New Interfacial Motifs and R-Dependent Photoluminescence122Hydride, chloride, and bromide show similar electronic effects in the Au 9 (PPh 3 ) 8 3+ nanocluster27Atomically precise alloy nanoclusters: syntheses, structures, and properties743Ligand-protected gold/silver superatoms: current status and emerging trends122Structure determination of a metastable Au 22 (SAdm) 16 nanocluster and its spontaneous transformation into Au 21 (SAdm) 1534Atomically Precise Alloy Nanoclusters98Controlling the Phosphine Ligands of Pt1Ag28(S-Adm)18(PR3)4 Nanoclusters25Understanding Doping Effects on Electronic Structures of Gold Superatoms: A Case Study of Diphosphine-Protected M@Au12 (M = Au, Pt, Ir)69Probing Pd n (n=1‐5) Clusters on Rutile TiO 2 Surfaces by Using First‐Principle Calculations5Modified Lennard‐Jones potentials for nanoscale atoms12Azide-Functionalized Nanoclusters via a Ligand-Induced Rearrangement14Toward Controlling the Electronic Structures of Chemically Modified Superatoms of Gold and Silver104Collision-Induced Reductive Elimination of 1,3-Diynes from [MAu24(C≡CR)18]2– (M = Pd, Pt) Yielding Clusters of Superatoms18Cocrystallization of Atomically Precise Nanoclusters43Controlled Dimerization and Bonding Scheme of Icosahedral M@Au 12 (M=Pd, Pt) Superatoms72Controlled Dimerization and Bonding Scheme of Icosahedral M@Au12 (M=Pd, Pt) Superatoms8Hydrido-coinage-metal clusters: Rational design, synthetic protocols and structural characteristics181Synergistic Effects of Pt and Cd Codoping to Icosahedral Au13 Superatoms51Controlling the Crystallographic Packing Modes of Pt 1 Ag 28 Nanoclusters: Effects on the Optical Properties and Nitrogen Adsorption–Desorption Performances17Atomically Precise Alloy Nanoclusters25Molecular reactivity of thiolate-protected noble metal nanoclusters: synthesis, self-assembly, and applications191Insights into the Metal-Exchange Synthesis of MAg24(SR)18 (M = Ni, Pd, Pt) Nanoclusters72Creation of active water-splitting photocatalysts by controlling cocatalysts using atomically precise metal nanoclusters58Controllable synthesis and formation mechanism study of homoleptic alkynyl-protected Au nanoclusters: recent advances, grand challenges, and great opportunities28[Cu23(PhSe)16(Ph3P)8(H)6]·BF4: Atomic-Level Insights into Cuboidal Polyhydrido Copper Nanoclusters and Their Quasi-simple Cubic Self-Assembly63An insight, at the atomic level, into the polarization effect in controlling the morphology of metal nanoclusters9Toward the creation of high-performance heterogeneous catalysts by controlled ligand desorption from atomically precise metal nanoclusters80Chemically Modified Gold/Silver Superatoms as Artificial Elements at Nanoscale: Design Principles and Synthesis Challenges280Ultrafast Size Expansion and Turn‐On Luminescence of Atomically Precise Silver Clusters by Hydrogen Sulfide138Ultrafast Size Expansion and Turn‐On Luminescence of Atomically Precise Silver Clusters by Hydrogen Sulfide14Thiolate‐Protected Metal Nanoclusters: Recent Development in Synthesis, Understanding of Reaction, and Application in Energy and Environmental Field136Gas-phase studies of chemically synthesized Au and Ag clusters33Cluster From Cluster: A Quantitative Approach to Magic Gold Nanoclusters [Au25(SR)18]−71Cluster From Cluster: A Quantitative Approach to Magic Gold Nanoclusters [Au25(SR)18]−10Magnetically induced currents and aromaticity in ligand-stabilized Au and AuPt superatoms14Atomically-ordered Trimetallic Superatoms M@Au6Ag6 (M = Pd, Pt): Synthesis and Photoluminescence Properties4Cubic aromaticity in ligand-stabilized doped Au superatoms17[Pt 2 Cu 34 (PET) 22 Cl 4 ] 2– : An Atomically Precise, 10-Electron PtCu Bimetal Nanocluster with a Direct Pt–Pt Bond84Probing Cluster−π Interactions between Cun– and C2H2/C2H4 for Gas Separation5Chemical transformations of [MAu8(PPh3)8]2+ (M = Pt, Pd) and [Au9(PPh3)8]3+ in methanol induced by irradiation of atmospheric pressure plasma6Assembling Silver Cluster-Based Organic Frameworks for Higher-Performance Hypergolic Properties33Ligand Effects on the Hydrogen Evolution Reaction Catalyzed by Au13 and Pt@Au12: Alkynyl vs Thiolate48Critical Role of CF3 Groups in the Electronic Stabilization of [PdAu24(C≡CC6H3(CF3)2)18]2– as Revealed by Gas-Phase Anion Photoelectron Spectroscopy15A reasonable approach for the generation of hollow icosahedral kernels in metal nanoclusters18Atomically Precise Synthesis of Chemically Modified Superatoms1Metal-nanocluster science and technology: my personal history and outlook29Targeted Synthesis of Ligand-Protected Gold Clusters and Exploration of Their Design Principles0Assembling Atomically Precise Noble Metal Nanoclusters Using Supramolecular Interactions51Anion‐Directed Regulation of Structures and Luminescence of Heterometallic Clusters9Anion‐Directed Regulation of Structures and Luminescence of Heterometallic Clusters35High-resolution crystal structure of a 20 kDa superfluorinated gold nanocluster23A Homoleptic Alkynyl‐Protected Au(I)9‐Ag(I)9 Cluster: Structure Analysis, Optical Properties, and Catalytic Implications9Doping‐Mediated Energy‐Level Engineering of M@Au 12 Superatoms (M=Pd, Pt, Rh, Ir) for Efficient Photoluminescence and Photocatalysis171Doping‐Mediated Energy‐Level Engineering of M@Au12 Superatoms (M=Pd, Pt, Rh, Ir) for Efficient Photoluminescence and Photocatalysis9Electron Affinities of Ligated Icosahedral M13 Superatoms Revisited by Gas-Phase Anion Photoelectron Spectroscopy23Mediating CO 2 Electroreduction Activity and Selectivity over Atomically Precise Copper Clusters29Mediating CO 2 Electroreduction Activity and Selectivity over Atomically Precise Copper Clusters182Atomically precise thiolate‐protected gold nanoclusters: Current status of designability of the structure and physicochemical properties85Hydrides, alkynyls, phosphines, and amines as ligands for nanoclusters0Nanocluster Transformation Induced by SbF 6 – Anions toward Boosting Photochemical Activities76Supervalence Bonding in Bi-icosahedral Cores of [M1Au37(SC2H4Ph)24]− (M = Pd and Pt): Fusion-Mediated Synthesis and Anion Photoelectron Spectroscopy27All-alkynyl-protected coinage metal nanoclusters: from synthesis to electrocatalytic CO 2 reduction applications43Elucidation of the electronic structures of thiolate-protected gold nanoclusters by electrochemical measurements13PtAg 18 superatoms costabilized by phosphines and halides: synthesis, structure, and catalysis8Recent developments in the investigation of driving forces for transforming coinage metal nanoclusters170The role of metal accessibility on carbon dioxide electroreduction in atomically precise nanoclusters18Spontaneous Intercluster Electron Transfer X 2– + X 0 → 2 X – (X = PtAu 24 (SC n H 2 n +1 ) 18 ) in Solution: Promotion by Long Alkyl Chains18Effect of Group-10 Element M (Ni, Pd, Pt) on Electronic Structure of Icosahedral M@Au 12 Cores of MAu 24 L 18 (L = Alkynyl, Thiolate)12(AuAg)44(SPhtBu)26 versus (AuAg)44(SPhF2)30: Tailoring the Geometric Structures and Optical Properties of Nanocluster Analogues5A Double Open-Shelled Au 43 Nanocluster with Increased Catalytic Activity and Stability54Anion-templated silver nanoclusters: precise synthesis and geometric structure27Catalysis Synergism by Atomically Precise Bimetallic Nanoclusters Doped with Heteroatoms128Solvent-induced reversible transformation between monomer-Ag32 and dimer-(Ag32)2 nanoclusters14Isomer-Selective Conversion of Au Clusters by Au(I) Thiolate Insertion4Directing Intrinsic Chirality in Gold Nanoclusters: Preferential Formation of Stable Enantiopure Clusters in High Yield and Experimentally Unveiling the “Super” Chirality of Au 14433Bonding and Electronic Interactions of Hydrogen with Gold Superatoms18Atomically precise Au and Ag nanoclusters doped with a single atom as model alloy catalysts50Cyclic ion mobility of doped [MAu 24 L 18 ] 2− superatoms and their fragments (M = Ni, Pd and Pt; L = alkynyl)18Tuning photoluminescence properties of Au clusters by surface modification and doping: lessons from case studies of icosahedral Au 1325Enantiopure Chiral Au 13 Nanoclusters Stabilized by Ditopic N -Heterocyclic Carbenes: Synthesis, Characterization, and Electrocatalytic Reduction of CO 231A 66‐Nuclear All‐Alkynyl Protected Peanut‐Shaped Silver(I)/Copper(I) Heterometallic Nanocluster: Intermediate in Copper‐Catalyzed Alkyne‐Azide Cycloaddition22Chemical Flexibility of Atomically Precise Metal Clusters280Atomically precise (AgPd)27 nanoclusters for nitrate electroreduction to NH3: Modulating the metal core by a ligand induced strategy19‘Passivated Precursor’ Approach to All‐Alkynyl‐Protected Gold Nanoclusters and Total Structure Determination of Au1309Gas‐Phase Anion Photoelectron Spectroscopy of Alkanethiolate‐Protected PtAu 12 Superatoms: Charging Energy in Vacuum vs Solution10Gas‐Phase Anion Photoelectron Spectroscopy of Alkanethiolate‐Protected PtAu12 Superatoms: Charging Energy in Vacuum vs Solution1Synthesis of N2-Type Superatomic Molecules26Synthesis of a Gold–Silver Alloy Nanocluster within a Ring‐Shaped Polyoxometalate and Its Photocatalytic Property2Synthesis of a Gold–Silver Alloy Nanocluster within a Ring‐Shaped Polyoxometalate and Its Photocatalytic Property60Atomically Precise Au24Pt(thiolate)12(ditholate)3 Nanoclusters with Excellent Electrocatalytic Hydrogen Evolution Reactivity1If the Crown Fits: Sterically Demanding N-Heterocyclic Carbene Promotes the Formation of Au8Pt Nanoclusters6Atomically Precise Au24Pt(thiolate)12(dithiolate)3 Nanoclusters with Excellent Electrocatalytic Hydrogen Evolution Reactivity47Resistance of a PdAu12(8e) Core to Growth in Collision-Induced Sequential Reductive Elimination of (C≡CR)2 from [PdAu24(C≡CR)18]2–9A comprehensive review of atomically precise metal nanoclusters with emergent photophysical properties towards diverse applications171An atomically precise Pt 17 nanocluster: its electronic structure and high activity for the hydrogen evolution reaction10Bonding Interaction in Heteronuclear Superatomic Molecules0Bonding Interaction in Homonuclear Superatomic Molecules0Effect of Ligand Substitution on Electron Affinities of Eight Electron Superatoms0Heteroatom number-dependent cluster frameworks in structurally comparable Pd–Au nanoclusters2Site-specific substitution in atomically precise carboranethiol-protected nanoclusters and concomitant changes in electronic properties41Atomically Engineered Trimetallic Nanoclusters Toward Enhanced Photoluminescence and Photoinitiation Activity22Density Functional Study on the Structures and Adsorption Properties of PtAgn (n = 1–16) Clusters5Shell engineering of an atomically precise PdH-doped Cu nanocluster0Efficient Electrocatalytic Semi‐Hydrogenation of Alkynes by Interfacial Engineering of Atomically Precise Silver Nanoclusters5Efficient Electrocatalytic Semi‐Hydrogenation of Alkynes by Interfacial Engineering of Atomically Precise Silver Nanoclusters29Cobalt-kernelled icosahedral gold nanocluster12Construction of Tunable Single-Atom Sites on Metal-Oxo Clusters for Enhanced CO2 Photoreduction1Transformation of [Au25(4-PyET)18]– into [Au20(4-PyET)14CN]– Induced by Atmospheric Pressure Plasma Irradiation in Methanol1Engineering Catalytic Efficiency by Thiolate-Protected Trimetallic (Cu, Pd, Au) Nanoclusters: Single-Atom Alloy Catalysts for Water–Gas Shift9Visualization of Total Synthesis from Au 11 to Au 13 Nanoclusters16X-ray Crystallographic Visualization of a Nucleation and Anisotropic Growth in Thiolate-Protected Gold Clusters: Toward Targeted Synthesis of Gold Quantum Needles33Superatomic or Not? A Case Study on Isostructural Au 3 Ag 2 and Au 3 Cu 2 Nanoclusters2Superatomic or Not? A Case Study on Isostructural Au 3 Ag 2 and Au 3 Cu 2 Nanoclusters1Electrocatalytic Nitrate Reduction Promoted by Atomically Precise Metal Nanoclusters3Assembling Ligand-Protected Gold Icosahedrons into Cyclic Superatomic Molecules with Superatomic Aromaticity1Leveraging chiral induced spin selectivity to improve the efficiency and selectivity of electrocatalytic reduction0Noncovalent Interaction‐Mediated Space Charge Transition Facilitated Isolated Copper(I)‐Iodide Clusters: Enabling High‐Resolution X‐Ray Imaging and Dynamic Encryption4Tunable atomically precise metal nanoclusters for sustainable electro- and photo-catalysis9Deepcluster agent to search global minimum of nanoclusters using deep reinforcement learning: A review1Tailoring the Electron Affinity of Au 13 Superhalogen via Ligand Design2Sequential Vertex-Specific Modulation of Enantiopure Metal Nanoclusters3Ligand engineering for active and durable, atomically-precise coinage-metal nanocluster catalysts4Creation of gold-based superatomic materials0Unraveling structure activity relationships inatomically precise metal nanoclusters for nitrate-to-ammonia electroreduction0

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  1. Alkynyl-Protected Au22(C≡CR)18 Clusters Featuring New Interfacial Motifs and R-Dependent Photoluminescence

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  2. Hydride, chloride, and bromide show similar electronic effects in the Au 9 (PPh 3 ) 8 3+ nanocluster

    Chemical Communications · 2019-12-23

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  4. Ligand-protected gold/silver superatoms: current status and emerging trends

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  5. Structure determination of a metastable Au 22 (SAdm) 16 nanocluster and its spontaneous transformation into Au 21 (SAdm) 15

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  6. Atomically Precise Alloy Nanoclusters

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  7. Controlling the Phosphine Ligands of Pt1Ag28(S-Adm)18(PR3)4 Nanoclusters

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  8. Understanding Doping Effects on Electronic Structures of Gold Superatoms: A Case Study of Diphosphine-Protected M@Au12 (M = Au, Pt, Ir)

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  9. Probing Pd n (n=1‐5) Clusters on Rutile TiO 2 Surfaces by Using First‐Principle Calculations

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  10. Modified Lennard‐Jones potentials for nanoscale atoms

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  11. Azide-Functionalized Nanoclusters via a Ligand-Induced Rearrangement

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  12. Toward Controlling the Electronic Structures of Chemically Modified Superatoms of Gold and Silver

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  13. Collision-Induced Reductive Elimination of 1,3-Diynes from [MAu24(C≡CR)18]2– (M = Pd, Pt) Yielding Clusters of Superatoms

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  14. Cocrystallization of Atomically Precise Nanoclusters

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  15. Controlled Dimerization and Bonding Scheme of Icosahedral M@Au 12 (M=Pd, Pt) Superatoms

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  16. Controlled Dimerization and Bonding Scheme of Icosahedral M@Au12 (M=Pd, Pt) Superatoms

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  17. Hydrido-coinage-metal clusters: Rational design, synthetic protocols and structural characteristics

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  18. Synergistic Effects of Pt and Cd Codoping to Icosahedral Au13 Superatoms

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  19. Controlling the Crystallographic Packing Modes of Pt 1 Ag 28 Nanoclusters: Effects on the Optical Properties and Nitrogen Adsorption–Desorption Performances

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  20. Atomically Precise Alloy Nanoclusters

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  21. Molecular reactivity of thiolate-protected noble metal nanoclusters: synthesis, self-assembly, and applications

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  22. Insights into the Metal-Exchange Synthesis of MAg24(SR)18 (M = Ni, Pd, Pt) Nanoclusters

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  23. Creation of active water-splitting photocatalysts by controlling cocatalysts using atomically precise metal nanoclusters

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  24. Controllable synthesis and formation mechanism study of homoleptic alkynyl-protected Au nanoclusters: recent advances, grand challenges, and great opportunities

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  25. [Cu23(PhSe)16(Ph3P)8(H)6]·BF4: Atomic-Level Insights into Cuboidal Polyhydrido Copper Nanoclusters and Their Quasi-simple Cubic Self-Assembly

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  26. An insight, at the atomic level, into the polarization effect in controlling the morphology of metal nanoclusters

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  27. Toward the creation of high-performance heterogeneous catalysts by controlled ligand desorption from atomically precise metal nanoclusters

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  28. Chemically Modified Gold/Silver Superatoms as Artificial Elements at Nanoscale: Design Principles and Synthesis Challenges

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  29. Ultrafast Size Expansion and Turn‐On Luminescence of Atomically Precise Silver Clusters by Hydrogen Sulfide

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  32. Gas-phase studies of chemically synthesized Au and Ag clusters

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  33. Cluster From Cluster: A Quantitative Approach to Magic Gold Nanoclusters [Au25(SR)18]−

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  34. Cluster From Cluster: A Quantitative Approach to Magic Gold Nanoclusters [Au25(SR)18]−

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  35. Magnetically induced currents and aromaticity in ligand-stabilized Au and AuPt superatoms

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  36. Atomically-ordered Trimetallic Superatoms M@Au6Ag6 (M = Pd, Pt): Synthesis and Photoluminescence Properties

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  37. Cubic aromaticity in ligand-stabilized doped Au superatoms

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  38. [Pt 2 Cu 34 (PET) 22 Cl 4 ] 2– : An Atomically Precise, 10-Electron PtCu Bimetal Nanocluster with a Direct Pt–Pt Bond

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  39. Probing Cluster−π Interactions between Cun– and C2H2/C2H4 for Gas Separation

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  40. Chemical transformations of [MAu8(PPh3)8]2+ (M = Pt, Pd) and [Au9(PPh3)8]3+ in methanol induced by irradiation of atmospheric pressure plasma

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  41. Assembling Silver Cluster-Based Organic Frameworks for Higher-Performance Hypergolic Properties

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  42. Ligand Effects on the Hydrogen Evolution Reaction Catalyzed by Au13 and Pt@Au12: Alkynyl vs Thiolate

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  43. Critical Role of CF3 Groups in the Electronic Stabilization of [PdAu24(C≡CC6H3(CF3)2)18]2– as Revealed by Gas-Phase Anion Photoelectron Spectroscopy

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  44. A reasonable approach for the generation of hollow icosahedral kernels in metal nanoclusters

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  45. Atomically Precise Synthesis of Chemically Modified Superatoms

    Unknown journal · 2021-10-29

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  46. Metal-nanocluster science and technology: my personal history and outlook

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  47. Targeted Synthesis of Ligand-Protected Gold Clusters and Exploration of Their Design Principles

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  48. Assembling Atomically Precise Noble Metal Nanoclusters Using Supramolecular Interactions

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  49. Anion‐Directed Regulation of Structures and Luminescence of Heterometallic Clusters

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    Jiaojiao Li, Chunyu Liu, Zong‐Jie Guan, Zhen Lei, Quan‐Ming Wang

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  50. Anion‐Directed Regulation of Structures and Luminescence of Heterometallic Clusters

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