ConspectusUnderstanding special stability of numerous ligand-protected gold nanoclusters has always been an active area of research. In the past few decades, several theoretical models, including the polyhedral skeletal electron pair theory (PSEPT), superatom complex (SAC), and superatom network (SAN), among others, have been developed for better understanding the stabilities and structures of selected ligand-protected gold nanoclusters. This Account overviews the recently proposed grand unified model (GUM) to offer some new insights into the structures and growth mechanism of nearly all crystallized and predicted ligand-protected gold nanoclusters.The main conceptual advancement of the GUM is identification of the duet and octet rules on the basis of the "big data" of 70+ reported ligand-protected gold nanoclusters. According to the two empirical rules, the cores of the gold nanoclusters can be regarded as being composed of two kinds of elementary blocks (namely, triangle Au3 and tetrahedron Au4), each having 2e closed-shell valence electrons (referred as Au3(2e) and Au4(2e)), as well as the secondary block (icosahedron Au13) with 8e closed-shell valence electrons (referred as Au13(8e)). The two elementary blocks (Au3(2e) and Au4(2e)) and the secondary block (Au13(8e)), from electron counting point of view, can be regarded as an analogy of the highly stable noble-gas atoms of He and Ne, respectively. In each elementary block, the Au atoms exhibit three different valence-electron states (i.e., 1e, 0.5e, and 0e), depending on the type of ligands bonded with these Au atoms. Such three valence-electron states are coined as three "flavors" of gold (namely, bottom, middle, and top "flavor"), a term borrowed from the quark model in the particle physics. Upon application of the duet and octet rules with accounting the three valence states of gold atoms, the Au3(2e), Au4(2e), and Au13(8e) blocks can exhibit 10 (denoted as Δ1-Δ10), 15 (denoted as T1-T15), and 91 (denoted as I1-I91) variants of valence states, respectively. When packing these blocks (with distinct electronic states) together, it forms the gold core of ligand-protected gold nanocluster. As such, the special stabilities of the ligand-protected gold nanoclusters are explained based on the local stability of each block. With GUM, rich and complex structures of ligand-protected gold nanoclusters have been analyzed through structure anatomy. Moreover, the growth of these clusters can be simply viewed as sequential addition of the blocks, rather than as addition of the gold atoms. Another useful application of the GUM is to analyze the structural isomerism. The three types of isomerism for the gold nanoclusters, i.e., core, staple, and complex isomerism, can be considered as an analogy of chain, point, and functional isomerism (known in organic chemistry), respectively. GUM can be applied to predict new clusters, thereby guiding experimental synthesis. Indeed, a number of ligand-protected gold nanoclusters with high stabilities were rationally designed based on the GUM.
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