Growth-Rule-Guided Structural Exploration of Thiolate-Protected Gold Nanoclusters

Understanding the structure and structure-property relationship of atomic and ligated clusters is one of the central research tasks in the field of cluster research. In chemistry, empirical rules such as the polyhedral skeleton electron pair theory (PSEPT) approach had been outlined to account for skeleton structures of many main-group atomic and ligand-protected transition metal clusters. Nonetheless, because of the diversity of cluster structures and compositions, no uniform structural and electronic rule is available for various cluster compounds. Exploring new cluster structures and their evolution is a hot topic in the field of cluster research for both experiment and theory. In this Account, we introduce our recent progress in the theoretical exploration of structures and evolution patterns of a class of atomically precise thiolate-protected gold nanoclusters using density functional theory computations. Unlike the conventional ligand-protected transition metal compounds, the thiolate-protected gold clusters demonstrate novel metal core/ligand shell interfacial structures in which the Au _m(SR) _n clusters can be divided into an ordered Au(0) core and a group of oligomeric SR[Au(SR)] _x ( x = 0, 1, 2, 3, ...) protection motifs. Guided by this "inherent structure rule", we have devised theoretical methods to rapidly explore cluster structures that do not necessarily require laborious global potential energy surface searches. The structural predictions of Au₃₈(SR)₂₄, Au₂₄(SR)₂₀, and Au₄₄(SR)₂₈ nanoclusters were completely or partially verified by the later X-ray crystallography studies. On the basis of the analysis of cluster structures determined by X-ray crystallography and theoretical prediction, a structural evolution diagram for the face-centered-cubic (fcc)-type Au _m(SR) _n clusters with m up to 92 has been preliminarily established. The structural evolution diagram indicates some basic structural and electronic evolution patterns of thiolate-protected gold nanoclusters. The fcc Au _m(SR) _n clusters show a genetic structural evolution pattern in which each step of cluster size increase results in the formation of another Au₄ tetrahedron or Au₃ triangle unit in the Au core, and every increase of a structural unit in the Au core leads to an increase of two electrons in the whole cluster. The unique one- or two-dimensional cluster size evolution, the isomerism of the Au-S framework, and the formation of a double-helical and cyclic tetrahedron network in the fcc Au _m(SR) _n clusters all can be addressed from this evolution pattern. The summarized cluster structural evolution diagrams enable us to further explore more stable cluster structures and understand their structure-electronic structure-property relationships.