Active Site Motifs in Atom‐Precise Coinage‐Metal Nanoclusters for Diverse Chemical Bond Construction

ABSTRACT Atom‐precise coinage‐metal nanoclusters (NCs) have emerged as a frontier platform in catalysis, enabling atomic‐level elucidation of structure–property relationships and rational design of next‐generation high‐performance catalysts. In this review, we propose a new classification framework for the active sites of coinage‐metal NCs, whereby the complex surface structures are categorized into three functional motifs: isolated, synergistic, and holistic motifs. This tripartite classification simplifies the structural complexity of cluster surfaces and offers a unified theoretical basis for understanding surface chemistry and designing diverse catalytic mechanisms. Within this framework, the review systematically summarizes key strategies for the controllable design of atom‐precise NCs, including geometrical optimization through surface engineering (defect and facet control), electronic tuning via heteroatom doping and ligand engineering, enhancement through metal‐metal and metal‐organic synergy, as well as dynamic regulation based on ligand dynamics. Focusing on precise chemical bond construction, we highlight the critical roles of these functional motifs in catalytic transformations, such as C−C bond formation, C−heteroatom coupling, and the assembly of complex multi‐bonded architectures. Representative research advances are discussed in detail from perspectives of structural features, catalytic performance, and underlying catalytic mechanisms, providing theoretical guidance for the rational design of efficient NC‐based catalysts. Overall, by establishing a unified classification system for active sites and conducting in‐depth analyses of reaction mechanisms and functional properties, this review aims to bridge key knowledge gaps in atom‐precise NC catalysis for organic bond formation, and to offer new theoretical insights for the rational design of novel high‐efficiency catalysts as well as the precise synthesis of complex organic molecules.