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.

Hybrid manganese halides have attracted widespread attention on account of their highly emissive optical properties. To understand the underlying structural factors that dictate the photoluminescence quantum yield (PLQY) of these materials, we report five new hybrid manganese bromides with the general formula AmMnBr4 [m = 1 or 2, A = dimethylammonium (DMA), 3methylpiperidinium (3-MP), 3-aminometylpiperidinium (3AMP), heptamethylenimine (HEP) and trimethylphenylammonium (TMPEA)]. By studying the crystal structures and optical properties of these materials and combining our results with the findings from previously reported analogs, we have found a direct correlation between Mn … Mn distance and the PLQY, where high PLQYs are associated with long Mn … Mn distances. This effect can be viewed as a manifestation of the concentration-quenching effect, except these are in stoichiometric compounds with precise interatomic distances, rather than random alloys. To gain better separation of the Mn centers and prevent energy transfer, a bulky singly-protonated cation that avoids H-bonding is ideal. We have demonstrated this principle in one of our newly reported material, (TMPEA)2MnBr4, where a PLQYs of 70.8 % for a powder sample and 98 % for a large single crystal sample is achieved. Our study reveals a generalized method for improving PLQYs in hybrid manganese bromides and is readily extended to designing all varieties of highly emissive hybrid materials.

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.

The larger size gold nanoparticles typically adopt a face-centered cubic (fcc) atomic packing, while in the ultrasmall nanoclusters the packing styles of Au atoms are diverse, including fcc, hexagonal close packing (hcp), and body-centered cubic (bcc), depending on the ligand protection. The possible conversion between these packing structures is largely unknown. Herein, we report the growth of a new Au21(S-Adm)15 nanocluster (S-Adm = adamantanethiolate) from Au18(SR)14 (SR = cyclohexylthiol), with the total structure determined by X-ray crystallography. It is discovered that the hcp Au9-core in Au18(SR)14 is transformed to a fcc Au10-core in Au21(S-Adm)15. Combining with density functional theory (DFT) calculations, we provide critical information about the growth mechanism (geometrical and electronic structure) and the origin of fcc-structure formation for the thiolate-protected gold nanoclusters.

The properties of metal materials can be greatly enriched by including various elements to generate alloys. The galvanic replacement represents a classical method for the preparation of both bulk-and nanoalloy materials. The difference of the electrochemical potential between the two metals acts as the driving force for the galvanic replacement reaction. However, this classical rule partially fails at the ultrasmall size scale, for that novel chemistry emerges by the decrease of the size of materials down to less than 3 nm due to the strong quantum effect. In this Account, we discuss an emerging topic of nanochemistry, the metal exchange in atomically precise ultrasmall (<3 nm) metal nanoparticles (or nanoclusters). The metal exchange method uses different types of metal sources (e.g., AuBrPPh 3 or AgSR complexes) to react with templating metal nanoclusters (e.g., Au 25 (SR) 18 − ), and finally alloy nanoclusters are produced. We demonstrate that the metal exchange reaction between metal nanoclusters and metal complexes does not follow the classical metal activity sequence (i.e., Fe > Cd > Co > Ni > Pb > Cu > Hg > Ag > Pd > Pt > Au) and such metal exchange reactions in the nanocluster range is, to a large extent, related with the electron shell closing and the structural stability of nanoclusters.In the subsequent sections, we present effective control over the number, position, and distribution of the dopants. The shape and structure of the final alloy products can be tailored by recently developed metal exchange methods. More importantly, modulation and enhancement of the properties of NCs through metal exchange are realized. For example, the largely increased quantum yield and the significantly improved catalytic activity. In addition, we shall also discuss the real-time characterization of the metal exchange reaction by the combination of UV−vis absorption spectroscopy, high resolution electrospray ionization mass spectrometry (ESI-MS), matrix assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF-MS), and single crystal X-ray diffraction (SC-XRD). By controlling the charge of the templating metal nanoclusters and the different types of metal complexes, the driving force of metal exchange has been studied, which is considered to be the thermodynamics rather than the electrochemical potential. In summary, the metal exchange reactions in the ultrasmall nanocluster range are totally different compared with the case of larger-sized metal nanoparticles. Depending on this novel method, atomically precise alloy nanoclusters can be prepared by reacting the nanocluster composed of inert metal (such as Au) with complexes of high-activity metals (e.g., Cd/Hg/Cu/Ag). We anticipate that future research on the metal exchange will contribute to the fundamental understanding of reaction behavior of metal atoms in ultrasmall nanoclusters and to the design of alloy nanoclusters with enhanced properties.