Hydride Doping of Chemically Modified Gold-Based Superatoms

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 clusters: a Au atom at a low-coordination site of a Au cluster can be replaced with a H atom while retaining the structural motif and electronic structure. However, this proposal has not been experimentally proved in chemically modified Au superatoms while a recent theoretical study predicted the formation of [HAu₂₅(SR)₁₈]⁰ (RS = thiolate). This Account summarizes our recent studies on the interaction of hydride(s) with two types of chemically modified Au-based superatoms: (1) the Au cores of [Au₉(PPh₃)₈]³⁺ and [PdAu₈(PPh₃)₈]²⁺ formally described as (Au₉)³⁺ and (PdAu₈)²⁺, respectively, and (2) Au₃₄ cluster stabilized by poly( N-vinyl-2-pyrrolidone) (PVP). The (Au₉)³⁺ and (PdAu₈)²⁺ cores correspond to oblate-shaped superatoms with six electrons and a coordinatively unsaturated site at the center, whereas the Au₃₄ cluster in PVP is viewed as a nearly spherical superatom having a closed electronic structure with 34 electrons and multiple uncoordinated sites on the surface. Through this study, we aimed to deepen our understanding on the role of a hydride in the formation processes of Au superatoms, the effect of adsorbed hydride(s) on the electronic structure of Au superatoms, and the activity of adsorbed hydrogen species for hydrogenation catalysis. Mass spectrometry and nuclear magnetic resonance spectroscopy demonstrated that a single hydride (H^-) was selectively doped to (Au₉)³⁺ and (PdAu₈)²⁺ upon reactions with BH₄^- to form (HAu₉)²⁺ and (HPdAu₈)⁺, respectively. Density functional theory (DFT) calculations showed that (HAu₉)²⁺ and (HPdAu₈)⁺ were more spherical than the original superatoms and had a closed electronic structure with eight electrons. The hydride-doped (HAu₉)²⁺ was selectively converted to the well-known (Au₁₁)³⁺ by electrophilic addition of two Au(I) units whereas (HPdAu₈)⁺ was converted to a new hydride-doped (HPdAu₁₀)³⁺. A two-step mechanism was proposed for hydride-mediated growth of Au-based superatoms: closure of the electronic structures by adsorption of a hydride, followed by the addition of two Au(I) units. The selective formation of Au₃₄ superatoms in PVP is also explained by assuming that hydride-doped Au clusters with 34 electrons were involved as key intermediates. The Au₃₄ superatom exhibited the localized surface plasmon resonance (LSPR) band by reacting with BH₄^- due to the electron donation by multiply adsorbed hydrides. The LSPR band disappeared by exposing hydride-doped Au₃₄ to dissolved O₂, but reappeared by reaction with BH₄^-. Catalysis for hydrogenation of C═C bonds was generated by doping a single Pd or Rh atom to Au₃₄. The results reported here demonstrate that the hydride doped to chemically modified Au superatoms mimics Au^- in terms of electron count. The hydride-mediated growth processes observed will contribute to the development of an atomically precise, bottom-up method of synthesizing new artificial elements in a periodic table for nanoscale materials. The interaction of hydride(s) with Au superatoms will find application in hydrogenation catalysis and hydrogen sensing.