The rod-shaped Au25 nanocluster possesses a low photoluminescence quantum yield (QY=0.1%) and hence is not of practical use in bioimaging and related applications. Herein, we show that substituting silver atoms for gold in the 25-atom matrix can drastically enhance the photoluminescence. The obtained Ag(x)Au(25-x) (x=1-13) nanoclusters exhibit high quantum yield (QY=40.1%), which is in striking contrast with the normally weakly luminescent Ag(x)Au(25-x) species (x=1-12, QY=0.21%). X-ray crystallography further determines the substitution sites of Ag atoms in the Ag(x)Au(25-x) cluster through partial occupancy analysis, which provides further insight into the mechanism of photoluminescence enhancement.

A metal exchange method based upon atomically precise gold nanoclusters (NCs) as templates is devised to obtain alloy NCs including CuxAu25-x(SR)18, AgxAu25-x(SR)18, Cd1Au24(SR)18, and Hg1Au24(SR)18 via reaction of the template with metal thiolate complexes of Cu(II), Ag(I), Cd(II), and Hg(II) (as opposed to common salt precursors such as CuCl2, AgNO3, etc.). Experimental results imply that the exchange between gold atoms in NCs and those of the second metal in the thiolated complex does not necessarily follow the order of metal activity (i.e., galvanic sequence). In addition, the crystal structure of the exchange product (Cd1Au24(SR)18) is successfully determined, indicating that the Cd is in the center of the 13-atom icosahedral core. This metal exchange method is expected to become a versatile new approach for synthesizing alloy NCs that contain both high- and low-activity metal atoms.

Decreasing the core size is one of the best ways to study the evolution from Au(I) complexes into Au nanoclusters. Toward this goal, we successfully synthesized the [Au18(SC6H11)14] nanocluster using the [Au18(SG)14] (SG=L-glutathione) nanocluster as the starting material to react with cyclohexylthiol, and determined the X-ray structure of the cyclohexylthiol-protected [Au18(C6H11S)14] nanocluster. The [Au18(SR)14] cluster has a Au9 bi-octahedral kernel (or inner core). This Au9 inner core is built by two octahedral Au6 cores sharing one triangular face. One transitional gold atom is found in the Au9 core, which can also be considered as part of the Au4(SR)5 staple motif. These findings offer new insight in terms of understanding the evolution from [Au(I)(SR)] complexes into Au nanoclusters.

We report the X-ray structure of a selenolate-capped Au24(SeR)20 nanocluster (R = C6H5). It exhibits a prolate Au8 kernel, which can be viewed as two tetrahedral Au4 units cross-joined together without sharing any Au atoms. The kernel is protected by two trimeric Au3(SeR)4 staple-like motifs as well as two pentameric Au5(SeR)6 staple motifs. Compared to the reported gold-thiolate nanocluster structures, the features of the Au8 kernel and pentameric Au5(SeR)6 staple motif are unprecedented and provide a structural basis for understanding the gold-selenolate nanoclusters.

Changes to surface motifs provide precise tailoring of nanoparticle properties.

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Gold-based materials hold promise in electrocatalytic reduction of CO2 to fuels. However, the polydispersity of conventional gold nanostructures limits mechanistic studies. Here, we report two types of atomically precise Au25 nanoclusters (1 nm) with distinct morphology (i.e., nanosphere and nanorod) for CO2 reduction catalysis. The Au25 nanosphere exhibits higher Faradaic efficiency for CO with higher formation rates compared to the Au25 nanorod. First-principles calculations reveal that the negative charge and the energetically favorable removal of one ligand to generate an active site on the nanosphere can better stabilize the important *COOH intermediate in CO2 electroreduction.

Crystallization-induced emission enhancement was achieved in metal nanoclusters for the first time.