Chemical Flexibility of Atomically Precise Metal Clusters

Abstract

Ligand-protected metal clusters possess hybrid properties that seamlessly combine an inorganic core with an organic ligand shell, imparting them exceptional chemical flexibility and unlocking remarkable application potential in diverse fields. Leveraging chemical flexibility to expand the library of available materials and stimulate the development of new functionalities is becoming an increasingly pressing requirement. This Review focuses on the origin of chemical flexibility from the structural analysis, including intra-cluster bonding, inter-cluster interactions, cluster-environments interactions, metal-to-ligand ratios, and thermodynamic effects. In the introduction, we briefly outline the development of metal clusters and explain the differences and commonalities of M(I)/M(I/ 0) coinage metal clusters. Additionally, we distinguish the bonding characteristics of metal atoms in the inorganic core, which give rise to their distinct chemical flexibility. Section 2 delves into the structural analysis, bonding categories, and thermodynamic theories related to metal clusters. In the following sections 3 to 7, we primarily elucidate the mechanisms that trigger chemical flexibility, the dynamic processes in transformation, the resultant alterations in structure, and the ensuing modifications in physical−chemical properties. Section 8 presents the notable applications that have emerged from utilizing metal clusters and their assemblies. Finally, in section 9, we discuss future challenges and opportunities within this area.

Extensive Polymerization of Atomically Precise Alloy Metal Clusters During Solid-State Reactions

“…Atomically precise metal clusters are a class of molecules that are well-known for their diverse properties. − Their structural integrity, composition, and electronic confinement make them promising candidates for various applications. − Over the past decade, exploring the reactions between atomically precise metal clusters has evolved as a new research area of interest. These reactions in the solution phase and in the gas phase have been probed using mass spectrometry. − In such reactions, the exchange of metal atoms and ligands occurs, while maintaining the nuclearity of individual clusters. − Neumaier et al have reported the kinetics of the reaction between the clusters [Au 25 (PET) 18 ] − and [Ag 25 (DMBT) 18 ] − in the solution .…”

Unveiling Complex Structural Features of Thiolate-Protected Gold Nanoclusters: From Internal Core to External “Staple” Motifs and Overall Charge States

“…Thiolate-protected gold nanoclusters (TP-AuNCs) have sparked immense interest for their distinctive quantum size phenomena, remarkable physicochemical attributes, and high potential for applications in fields like optics and biomedicine. − The remarkable progress in TP-AuNCs has ignited fervent interest among experimental scientists in crystalline structure preparation. − Specifically, since Kornberg et al successfully resolved the first crystal structure of the TP-AuNC Au 102 (SR) 44 (SR = thiolate ligand), numerous other structures of TP-AuNCs have been crystallized. ,− The successful characterization of these crystalline structures reveals that TP-AuNCs of various sizes and morphologies consist of internal gold cores, external “staple” motifs SR[Au(SR)] x (x = 0, 1, 2, 3, ...), and overall charge states. , …”