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The reduction of alkynyl‐silver and phosphine‐silver precursors with a weak reducing reagent Ph2SiH2 led to the formation of a novel silver nanocluster [Ag93(PPh3)6(C≡CR)50]3+ (R=4‐CH3OC6H4), which is the largest structurally characterized cluster of clusters. This disc‐shaped cluster has a Ag69 kernel consisting of a bicapped hexagonal prismatic Ag15 unit wrapped by six Ino decahedra through edge‐sharing. This is the first time that Ino decahedra are used as a building block to assemble a cluster of clusters. Moreover, the central silver atom has a coordination number of 14, which is the highest in metal nanoclusters. This work provides a diverse metal packing pattern in metal nanoclusters, which is helpful for understanding metal cluster assembling mechanisms. [ABSTRACT FROM AUTHOR]

Anions have been used to regulate the structures and luminescence of heterometallic clusters. Introducing ClO4− into orange‐emissive, butterfly‐like [(C)(Au‐PPhpy2)6Ag4](BF4)6 (1, PPhpy2=bis(2‐pyridyl)phenylphosphine) leads to the formation of red‐emissive [(C)(Au‐PPhpy2)6Ag5(ClO4)3](ClO4)4 (2) with a novel trigonal bipyramidal structure; employing PhCO2− gives yellow‐emissive, hexagram‐like [(C)(Au‐PPhpy2)6Ag6(PhCO2)3](BF4)5 (3). Notably, 1 exhibits weak luminescence in CH2Cl2/CH3OH=1 : 1 (v : v) with a quantum yield (QY) of 0.05, whereas it was dramatically increased to 0.49 and 0.83 for 2 and 3, respectively. Theoretical calculation confirms that the involvement of anions in the electronic structures is responsible for the shifts of emission. The high QYs of 2 and 3 are attributed to the protection provided by ligands and anions. This work demonstrates that anions may serve as an extra designable factor beyond just counterions for functional metal clusters. [ABSTRACT FROM AUTHOR]

By directly reducing alkynyl–silver precursors, we successfully obtained a large alkynyl‐protected silver nanocluster, (C7H17ClN)3[Ag112Cl6(C≡CAr)51], which is hitherto the largest structurally characterized silver nanocluster in the alkynyl family. The cluster exhibits four concentric core–shell structures (Ag13@Ag42@Ag48@Ag9), and four types of alkynyl–silver binding modes are observed. Chloride was found to be critical for the stabilization and formation of the silver nanocluster. The release of chloride ions in situ from CH2Cl2 solvent has been confirmed by mass spectrometry. This study suggests that the combination of alkynyl and halide ligands will pave a new way for the synthesis of large silver nanoclusters. [ABSTRACT FROM AUTHOR]

By directly reducing alkynyl–silver precursors, we successfully obtained a large alkynyl‐protected silver nanocluster, (C7H17ClN)3[Ag112Cl6(C≡CAr)51], which is hitherto the largest structurally characterized silver nanocluster in the alkynyl family. The cluster exhibits four concentric core–shell structures (Ag13@Ag42@Ag48@Ag9), and four types of alkynyl–silver binding modes are observed. Chloride was found to be critical for the stabilization and formation of the silver nanocluster. The release of chloride ions in situ from CH2Cl2 solvent has been confirmed by mass spectrometry. This study suggests that the combination of alkynyl and halide ligands will pave a new way for the synthesis of large silver nanoclusters. [ABSTRACT FROM AUTHOR]

We report the total structure determination of a covalently bonded nanocluster polymer [Au7Ag9(dppf)3(CF3CO2)7BF4]n (1). This features a one-dimensional linear chain, consisting of unique molecular building blocks, Au7Ag8(dppf)3(CF3CO2)7 clusters, which are linked together by Ag–O bonds rather than Au–Au interactions or bidentate organic bridges as previously reported. [ABSTRACT FROM AUTHOR]

Abstract: The controlled synthesis and structure determination of a bimetallic nanocluster Au57Ag53(C≡CPh)40Br12 (Au57Ag53) is presented. The metal core has a four‐shell Au2M3@Au34@Ag51 @Au20 (M=1/3 Au+2/3 Ag) architecture. In contrast to the previously reported large nanoclusters that have highly symmetric kernel structures, the metal atoms in Au57Ag53 are arranged in an irregular manner with C1 symmetry. This cluster exhibits excellent thermal stability and is robust under oxidative or basic conditions. The silver precursors play a key role in dictating the structures of the nanoclusters, which suggests the importance of the counteranions used. [ABSTRACT FROM AUTHOR]

An intensely luminescent gold(I)-silver(I) cluster [(C)(AuPPhpy2)6Ag6(CF3CO2)3](BF4)5 (PPhpy2=bis(2-pyridyl)phenylphosphine) ( 3) is synthesized by the reaction of [(C)(AuPPhpy2)6Ag4](BF4)6 with AgCF3CO2. All eight faces of the octahedral C@Au6 core in 3 are capped, that is, six faces are capped by silver ions and two by tetrafluoroborates. Cluster 3 is intensely luminescent in solution with a quantum yield of 92 %. Ligation of CF3CO2− ions is vital for the construction and emission properties of 3, as confirmed by DFT calculations. BF4− ions are involved in the protecting sphere of the metal core, as evidenced by 19F NMR data. The participation of phosphines, CF3CO2−, and BF4− ions in the protection of the emissive core and the enhancement of the rigidity of the cluster result in the high emission efficiency. This is the first example of organic ligands and inorganic anions forming a rigid protecting sphere for luminescent coinage-metal clusters. [ABSTRACT FROM AUTHOR]

A red-near-IR dual-emissive nanocluster with the composition [Au10Ag2(2-py−C≡C)3(dppy)6](BF4)5 ( 1; 2-py−C≡C is 2-pyridylethynyl, dppy=2-pyridyldiphenylphosphine) has been synthesized. Single-crystal X-ray structural analysis reveals that 1 has a trigonal bipyramidal Au10Ag2 core that contains a planar Au4(2-py−C≡C)3 unit sandwiched by two Au3Ag(dppy)3 motifs. Cluster 1 shows intense red-NIR dual emission in solution. The visible emission originates from metal-to-ligand charge transfer (MLCT) from silver atoms to phosphine ligands in the Au3Ag(dppy)3 motifs, and the intense NIR emission is associated with the participation of 2-pyridylethynyl in the frontier orbitals of the cluster, which is confirmed by a time-dependent density functional theory (TD-DFT) calculation. [ABSTRACT FROM AUTHOR]

Surface organic ligands are critical in determining the formation and properties of atomically precise metal nanoclusters. In contrast to the conventionally used thiolate, phosphine and alkynyl ligands, the amine ligand dipyridylamine is applied here as a protecting agent in the synthesis of atomically precise metal nanoclusters. We report two homoleptic amido-protected Ag nanoclusters as examples of all-nitrogen-donor-protected metal nanoclusters: [Ag21(dpa)12]SbF6 (Ag21) and [Ag22(dpa)12](SbF6)2 (Ag22) (dpa = dipyridylamido). Single crystal X-ray structural analysis reveals that both clusters consist of a centered-icosahedron Ag13 core wrapped by 12 dpa ligands. The flexible arrangement of the N donors in dpa facilitates the solvent-triggered reversible interconversion between Ag21 and Ag22 due to their very different solubility. The successful use of dpa in the synthesis of well-defined silver nanoclusters may motivate more studies on metal nanoclusters protected by amido type ligands. Noble metal nanoclusters are commonly protected by thiolate, phosphine, or alkynyl ligands. Here, the authors synthesize two homoleptic amido-protected silver clusters, whose structures interconvert easily with changes of solvent due to the coordination flexibility and diverse binding modes of the nitrogen-donor ligands. [ABSTRACT FROM AUTHOR]

By directly reducing alkynyl–silver precursors, we successfully obtained a large alkynyl‐protected silver nanocluster, (C7H17ClN)3[Ag112Cl6(C≡CAr)51], which is hitherto the largest structurally characterized silver nanocluster in the alkynyl family. The cluster exhibits four concentric core–shell structures (Ag13@Ag42@Ag48@Ag9), and four types of alkynyl–silver binding modes are observed. Chloride was found to be critical for the stabilization and formation of the silver nanocluster. The release of chloride ions in situ from CH2Cl2 solvent has been confirmed by mass spectrometry. This study suggests that the combination of alkynyl and halide ligands will pave a new way for the synthesis of large silver nanoclusters. [ABSTRACT FROM AUTHOR]

By directly reducing alkynyl–silver precursors, we successfully obtained a large alkynyl‐protected silver nanocluster, (C7H17ClN)3[Ag112Cl6(C≡CAr)51], which is hitherto the largest structurally characterized silver nanocluster in the alkynyl family. The cluster exhibits four concentric core–shell structures (Ag13@Ag42@Ag48@Ag9), and four types of alkynyl–silver binding modes are observed. Chloride was found to be critical for the stabilization and formation of the silver nanocluster. The release of chloride ions in situ from CH2Cl2 solvent has been confirmed by mass spectrometry. This study suggests that the combination of alkynyl and halide ligands will pave a new way for the synthesis of large silver nanoclusters. [ABSTRACT FROM AUTHOR]

Small anions play a big role in the preparation of an intensely luminescent gold(I)–silver(I) cluster. In their Communication on page 7117 ff. Q.‐M. Wang and co‐workers show that the stepwise addition of silver ions to the gold‐cluster precursor enhances the rigidity of the cluster. The emissive core is fully protected by organic ligands and inorganic anions, which results in high emission efficiency. [ABSTRACT FROM AUTHOR]