Shinjiro Takano

Pure and doped gold/silver clusters protected by monolayers of organic ligands have attracted much interest as novel functional materials owing to their nonbulk-like, size-specific properties. They can be viewed as chemically modified superatoms because their stabilities and properties are governed by the electron shell configurations of the Au/Ag cores. Chemically modified superatoms are unique from conventional atoms in that they have additional control parameters such as surface modification,

A series of doped gold superatoms M@Au₁₂ (M = Ru, Rh, Ir) was synthesized by capping with the bidentate ligand (Ph₂)PCH₂P(Ph₂). A single-crystal X-ray diffraction analysis showed that all the M@Au₁₂ superatoms had icosahedral motifs with a significantly higher symmetry than that of the pure Au₁₃ counterpart due to different coordination geometries. The Ru@Au₁₂ superatom exhibited a room-temperature phosphorescence with

Atomically size-selected gold (Au) clusters protected by organic ligands or stabilized by polymers provide an ideal platform to test fundamental concepts and size-specific phenomena, such as the superatomic concept and metal-to-nonmetal transition. Recent studies revealed that these stabilized Au clusters take atomlike quantized electronic structures and can be viewed as chemically modified Au superatoms. An analogy between Au and hydrogen (H) atoms is an interesting proposal made for bare Au cl

Doping of a hydride (H^-) into an oblate-shaped gold cluster [Au₉(PPh₃)₈]³⁺ was observed for the first time by mass spectrometry and NMR spectroscopy. Density functional theory calculations for the product [Au₉H(PPh₃)₈]²⁺ demonstrated that the (Au₉H)²⁺ core can be viewed as a nearly spherical superatom with a closed electronic shell. The hydride-doped superatom (Au₉H

An efficient and selective method was developed for the synthesis of bimetallic clusters, MAu₂₄L₁₈ (M = Pd or Pt; L = thiolates or alkynyls), by the reaction of Au(I)L oligomers with quasi-spherical superatoms [HMAu₈(PPh₃)₈]⁺ activated by hydride doping. This hydride-mediated conversion afforded previously known clusters MAu₂₄(SC₂H₄Ph)₁₈ having an icosahedral (M@Au₁₂)<sup>6+</

A hydride (H^-)-doped bimetallic superatom (HPdAu₈)⁺ was produced by reacting BH₄^- with an oblate (PdAu₈)²⁺ superatom protected by PPh₃. The H atom in (HPdAu₈)⁺ survived during the sequential addition of Au(I)Cl to form an (HPdAu₁₀)³⁺ superatom, in sharp contrast to the proton release from a H^--doped pure gold superatom (HAu₉)²⁺ in th

Despite recent progress in the synthesis and characterization of optically active gold clusters, the factor determining optical rotatory strength has not been clarified due to the lack of structurally resolved, enantiomerically pure Au clusters. We addressed this issue by studying the correlation between the optical activity and geometrical structures of two types of Au clusters that were protected by chiral diphosphines: [Au₁₁(R/S-DIOP)₄Cl₂]⁺ (DIOP =

Slow reduction of Au ions in the presence of 4-(2-mercaptoethyl)benzoic acid (4-MEBA) gave Au76(4-MEBA)44 clusters that exhibited a strong (3 × 10(5) M(-1) cm(-1)) near-infrared absorption band at 1340 nm. Powder X-ray diffraction studies indicated that the Au core has a one-dimensional fcc structure that is elongated along the {100} direction.

Targeted syntheses of MM'Au₃₆ (PET)₂₄ (M, M'=Pd, Pt; PET=SC₂ H₄ Ph) were achieved by hydride-mediated fusion reactions between [MAu₈ (PPh₃ )₈ ]²⁺ and [M'Au₂₄ (PET)₁₈ ]^- . Single-crystal X-ray diffraction analysis indicated that the products have bi-icosahedral MM'Au₂₁ cores composed of M@Au₁₂ and M'@Au₁₂ superatoms. Although the MM'Au<sub>21</s