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

Abstract

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, compositions, atomic packing, and size, although both of them follow similar Aufbau principles. Atomically precise synthesis and structure determination by X-ray crystallography have deepened our understanding of the correlation between the structures and fundamental properties of the superatoms. However, remaining challenges for the exploration of novel materials using superatoms as artificial elements at the nanoscale include (1) establishment of guiding principles of the electronic structures and (2) development of efficient, targeted synthesis according to rational design guidelines for functionalities. To address the first task, we herein propose and rationalize empirical guiding principles of electronic structures using icosahedral Au 13 /Ag 13 superatoms with the closed electron configuration as platforms. The second task is addressed by proposing design guidelines for functionalities and hydride-mediated transformation processes for efficient, targeted synthesis. These efforts will lead to the construction of a new periodic table of chemically modified superatoms and open up a materials world of quasi-molecules made of superatoms. We hope that this Perspective will contribute to the creation of a new paradigm based on superatoms, which parallels the matured world of molecular science.

Creation of High‐Performance Heterogeneous Photocatalysts by Controlling Ligand Desorption and Particle Size of Gold Nanocluster

“…The findings obtained in this study are expected to provide clear design guidelines for the creation of highly functional heterogeneous catalysts using metal NCs, which have been reported thus far. [ 12 , 60 , 61 ]…”

Au70S20(PPh3)12 as Superatomic Analog to 18‐electron Transition‐Metal Complexes

“…Four related LMO's oriented at about 124°from each other leading to a quasi tetrahedral arrangement are depicted, accounting for a set of four SP 3 -hybridized orbitals within the core. In addition, a set of five orbitals was obtained, accounting for the 1D 10 state. Within the current perspective based on the Au 22 4 + core, such a picture resembles the classical tetrahedral Ni(CO) 4 complex involving a sp 3 -hybridization of nickel 4s-and 4p-shells responsible for the stabilization of the CO-coordination, and the non-bonding 3d-Ni shells.…”

Catalytic Conversion of C 1 Molecules on Atomically Precise Metal Nanoclusters

“…To date, significant achievements have been made toward the atomically precise metal nanoclusters in terms of synthesis, characterization and structure-reactivity relationship, and the relevant progresses can be summarized in recent reviews. [13][14][15][16][17][18][19][20][21][22][23][24][25] However, less summary and perspective have been made in the C 1 transformation catalyzed by metal nanoclusters. In this review, research processes of nanoclusters for C 1 conversion are highlighted, including thermal-driven reaction processes, such as CO Au 25 (SNap) 18 and Au 25 (PPh 3 ) 10 (PET) 5 X 2 and the large ligand steric hindrance of Au 25 (PPh 3 ) 10 (PET) 5 X 2 .…”

“…8a), implying that the coordinatively unsaturated (cus) gold atoms (Figure 8b) in the fresh Au 22 were active at low-temperature. DFT calculations revealed that the cus gold sites in the fresh Au 22 This article presented here has been accepted for publication in CCS Chemistry and is posted at the © 2021 Chinese Chemical Society.…”