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RESEARCH PAPER · Inorganic Chemistry · 2020

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

Haru Hirai, Shinjiro Takano, Toshikazu Nakamura, Tatsuya Tsukuda

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Understanding Doping Effects on Electronic Structures of Gold Superatoms: A Case Study of Diphosphine-Protected M@Au12 (M = Au, Pt, Ir)OriginalToward Controlling the Electronic Structures of Chemically Modified Superatoms of Gold and Silver104Synergistic Effects of Pt and Cd Codoping to Icosahedral Au13 Superatoms51Doping Effect on the Magnetism of Thiolate-Capped 25-Atom Alloy Nanoclusters34Atom-by-Atom Evolution of the Same Ligand-Protected Au 21 , Au 22 , Au 22 Cd 1 , and Au 24 Nanocluster Series53Observable but Not Isolable: The RhAu 24 (PET) 18 1+ Nanocluster11Creation of active water-splitting photocatalysts by controlling cocatalysts using atomically precise metal nanoclusters58Electron Counting in Ligated High Nuclearity Late Transition Metal Clusters12Instrument Center, Institute for Molecular Science0Toward 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 Challenges280Thiolate‐Protected Metal Nanoclusters: Recent Development in Synthesis, Understanding of Reaction, and Application in Energy and Environmental Field136Atomically-ordered Trimetallic Superatoms M@Au6Ag6 (M = Pd, Pt): Synthesis and Photoluminescence Properties4On Heteronuclear Isoelectronic Alternatives to [Au13(dppe)5Cl2]3+: Electronic and Optical Properties of the 18-Electron Os@[Au12(dppe)5Cl2] Cluster from Relativistic Density Functional Theory Computations14Superatom‐in‐Superatom [RhH@Ag 24 (SPhMe 2 ) 18 ] 2− Nanocluster66Superatom‐in‐Superatom [RhH@Ag24(SPhMe2)18]2− Nanocluster9Photoluminescence of Doped Superatoms M@Au 12 (M = Ru, Rh, Ir) Homoleptically Capped by (Ph 2 )PCH 2 P(Ph 2 ): Efficient Room-Temperature Phosphorescence from Ru@Au 12156Diarsine- vs diphosphine-protected Au13 clusters: Effect of subtle geometric differences on optical property and electronic structure17Gold Clusters: From the Dispute on a Gold Chair to the Golden Future of Nanostructures3Atomically 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 Principles0A Review of State of the Art in Phosphine Ligated Gold Clusters and Application in Catalysis130Doping‐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 Photocatalysis9Enhanced Fluorescence with Tunable Color in Doped Diphosphine-Protected Gold Nanoclusters29Atomically precise thiolate‐protected gold nanoclusters: Current status of designability of the structure and physicochemical properties85Theoretical and experimental study of organometallic transition metal nanoclusters and nanoparticles0The bandgap of sulfur-doped Ag 2 O nanoparticles27All-alkynyl-protected coinage metal nanoclusters: from synthesis to electrocatalytic CO 2 reduction applications43Elucidation of the electronic structures of thiolate-protected gold nanoclusters by electrochemical measurements13IrAu 12 superatom modified by chiral diphosphines: doping-induced enhancement of chiroptical activity22Monoarsine-protected icosahedral cluster [Au 13 (AsPh 3 ) 8 Cl 4 ] + : comparative studies on ligand effect and surface reactivity with its stibine analogue17Physical-chemical properties of metal nanoclusters0From 8- to 18-Cluster Electrons Superatoms: Evaluation via DFT Calculations of the Ligand-Protected W@Au12(dppm)6 Cluster Displaying Distinctive Electronic and Optical Properties20Effect 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)12Superatom‐in‐Superatom Nanoclusters: Synthesis, Structure, and Photoluminescence30Superatom‐in‐Superatom Nanoclusters: Synthesis, Structure, and Photoluminescence5Hydride Doping Effects on the Structure and Properties of Eight-Electron Rh/Ag Superatoms: The [RhH x @Ag 21– x {S 2 P(O n Pr) 2 } 12 ] ( x = 0–2) Series40A Computational Exploration of Exohedrally Transition Metal Doped Si94– Superatom Based Magnetic MSi9M′ Clusters (M, M′ = Sc(II) to Cu(II))4Core-Packing-Related Vibrational Properties of Thiol-Protected Gold Nanoclusters and Their Excited-State Behavior18“Sergeants-and-soldiers” principle in the synthesis of intrinsically chiral Au 13 clusters3Atomically precise Au and Ag nanoclusters doped with a single atom as model alloy catalysts50Doping-mediated excited state dynamics of diphosphine-protected M@Au 12 (M = Au, Ir) superatom nanoclusters11Stability prediction of gold nanoclusters with different ligands and doped metals: deep learning and experimental tests35Synthesis of RhH-doped Au–Ag alloy nanoclusters and dopant evolution3Triplet–triplet annihilation-based photon upconversion using nanoparticles and nanoclusters36Tuning photoluminescence properties of Au clusters by surface modification and doping: lessons from case studies of icosahedral Au 1325Introducing Iodide Ligands on IrAu 12 Cluster Enhances Phosphorescence Efficiency and Photoredox Activity11Diphosphine‐Protected IrAu12 Superatom with Open Site(s): Synthesis and Programmed Stepwise Assembly0Diphosphine‐Protected IrAu12 Superatom with Open Site(s): Synthesis and Programmed Stepwise Assembly31A nearly perfect icosahedral Ir@Au 12 superatom with superior photoluminescence obtained by ligand engineering14Cobalt-kernelled icosahedral gold nanocluster12Construction of Tunable Single-Atom Sites on Metal-Oxo Clusters for Enhanced CO2 Photoreduction1Visualization of Total Synthesis from Au 11 to Au 13 Nanoclusters16Superatomic 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 Nanoclusters1Fully Reversible Photoelectronic Switching Enabled by Delocalized Excitons in a Single Superatom Junction7Computational exploration of N-heterocyclic carbene (NHC)-for-phenylacetylene ligand exchange in IrAu 12 alloy clusters1Photoluminescence of ligand-protected gold nanoclusters: progress in experimental and theoretical studies5Superatomic interconversion causes reversible on–off luminescence of doped silver nanoclusters1Theoretical Insights on the Regulatory Mechanisms of Structure and Doping on the Photoluminescence of Ligand Protected Gold Nanoclusters6Ion Mobility–Mass Spectrometry: A Powerful Platform for Structural Characterization of Metal Nanoclusters0Rational Design of Single-Atom Alloy Catalysts from PtAu 24 Nanoclusters toward Enhanced Electrochemical Activity4Ligand-Induced Structural Evolution and Luminescence Tuning in a Series of Superatomic Ir/Ag Hydride-Containing Nanoclusters1Synthesis of Luminescent Metal Nanoclusters with Atomically Precise Structures and High Quantum Yields0Gold Clusters With Open‐Shell Ligands: Superatom Mediated Magnetic Interaction0Gold Clusters With Open‐Shell Ligands: Superatom Mediated Magnetic Interaction0Emergence of Nido -Icosahedral Superatomic Units in Iridium-Doped Silver Cluster Assemblies0Beyond the Metal Core: Platinum Incorporation Reshapes Redox Levels and Ligand Shells in Au 25 Thiolate Clusters0

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

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

    The Journal of Physical Chemistry C · 2020-10-15

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  3. Doping Effect on the Magnetism of Thiolate-Capped 25-Atom Alloy Nanoclusters

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    Yingwei Li, Saborni Biswas, Tian‐Yi Luo, Rosalba Juarez‐Mosqueda, Michael G. Taylor, Giannis Mpourmpakis, Nathaniel L. Rosi, Michael P. Hendrich, Rongchao M. Jin

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  4. Atom-by-Atom Evolution of the Same Ligand-Protected Au 21 , Au 22 , Au 22 Cd 1 , and Au 24 Nanocluster Series

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  5. Observable but Not Isolable: The RhAu 24 (PET) 18 1+ Nanocluster

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

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  7. Electron Counting in Ligated High Nuclearity Late Transition Metal Clusters

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  8. Instrument Center, Institute for Molecular Science

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

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

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  11. Thiolate‐Protected Metal Nanoclusters: Recent Development in Synthesis, Understanding of Reaction, and Application in Energy and Environmental Field

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

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  13. On Heteronuclear Isoelectronic Alternatives to [Au13(dppe)5Cl2]3+: Electronic and Optical Properties of the 18-Electron Os@[Au12(dppe)5Cl2] Cluster from Relativistic Density Functional Theory Computations

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  14. Superatom‐in‐Superatom [RhH@Ag 24 (SPhMe 2 ) 18 ] 2− Nanocluster

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  16. Photoluminescence of Doped Superatoms M@Au 12 (M = Ru, Rh, Ir) Homoleptically Capped by (Ph 2 )PCH 2 P(Ph 2 ): Efficient Room-Temperature Phosphorescence from Ru@Au 12

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    Shinjiro Takano, Haru Hirai, Takuya Nakashima, Takeshi Iwasa, Tetsuya Taketsugu, Tatsuya Tsukuda

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  17. Diarsine- vs diphosphine-protected Au13 clusters: Effect of subtle geometric differences on optical property and electronic structure

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  18. Gold Clusters: From the Dispute on a Gold Chair to the Golden Future of Nanostructures

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  19. Atomically Precise Synthesis of Chemically Modified Superatoms

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

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

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  22. A Review of State of the Art in Phosphine Ligated Gold Clusters and Application in Catalysis

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  23. Doping‐Mediated Energy‐Level Engineering of M@Au 12 Superatoms (M=Pd, Pt, Rh, Ir) for Efficient Photoluminescence and Photocatalysis

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  24. Doping‐Mediated Energy‐Level Engineering of M@Au12 Superatoms (M=Pd, Pt, Rh, Ir) for Efficient Photoluminescence and Photocatalysis

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  25. Enhanced Fluorescence with Tunable Color in Doped Diphosphine-Protected Gold Nanoclusters

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  26. Atomically precise thiolate‐protected gold nanoclusters: Current status of designability of the structure and physicochemical properties

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  34. From 8- to 18-Cluster Electrons Superatoms: Evaluation via DFT Calculations of the Ligand-Protected W@Au12(dppm)6 Cluster Displaying Distinctive Electronic and Optical Properties

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  35. Effect 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)

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  38. Hydride Doping Effects on the Structure and Properties of Eight-Electron Rh/Ag Superatoms: The [RhH x @Ag 21– x {S 2 P(O n Pr) 2 } 12 ] ( x = 0–2) Series

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  40. Core-Packing-Related Vibrational Properties of Thiol-Protected Gold Nanoclusters and Their Excited-State Behavior

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  41. “Sergeants-and-soldiers” principle in the synthesis of intrinsically chiral Au 13 clusters

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  43. Doping-mediated excited state dynamics of diphosphine-protected M@Au 12 (M = Au, Ir) superatom nanoclusters

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  47. Tuning photoluminescence properties of Au clusters by surface modification and doping: lessons from case studies of icosahedral Au 13

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  48. Introducing Iodide Ligands on IrAu 12 Cluster Enhances Phosphorescence Efficiency and Photoredox Activity

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  49. Diphosphine‐Protected IrAu12 Superatom with Open Site(s): Synthesis and Programmed Stepwise Assembly

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  50. Diphosphine‐Protected IrAu12 Superatom with Open Site(s): Synthesis and Programmed Stepwise Assembly

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