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The superatomic orbital splitting (SOS) method is developed to understand the electronic structures of coinage metal nanoclusters, in which delocalized electron counts are not magic numbers. Because the symmetry of a metal core can significantly affect the electronic structure of a nanocluster, this method takes the shape of the core into account in determining the order of group orbital levels. By taking nanoclusters as superatoms, a highly positively charged core is established by removing the ligands and staples. The superatomic orbitals split into group orbitals at different energy levels because of the nonspherical shape of the cluster core. Therefore, the electron configuration of the nonmagic-number nanocluster can be qualitatively analyzed without quantum chemical calculations, which is very important for understanding the stability of the cluster.

For the first time site-specific doping of silver into a spherical Au25 nanocluster has been achieved in [Au19Ag6(MeOPhS)17(PPh3)6] (BF4)2. It is a 6e system showing quite a different absorption spectrum from [Au25(SR)18]−.

A Au55 nanocluster with the composition of [Au55 (p-MBT)24 (Ph3 P)6 ](SbF6 )3 (p-MBT=4-methylbenzenethiolate) is synthesized via direct reduction of gold-phosphine and gold-thiolate precursors. Single-crystal X-ray diffraction reveals that this Au55 nanocluster features a face-centered cubic (fcc) Au55 kernel, different from the well-known two-shell cuboctahedral arrangement in Au55 (Ph3 P)12 Cl6 . The Au55 cluster shows a wide optical absorption band with optical energy gap (Eg =1.28 eV). It is found that the exclusion of chloride is crucial for the formation of the title cluster, otherwise rod-like [Au25 (SR)5 (PPh3 )10 Cl2 ]2+ is obtained. The strategy to run synthetic reaction in the absence of halide leads to new members of phosphine/thiolate co-protected metal nanoclusters. The Au55 nanocluster exhibits high catalytic activity and selectivity for electrochemical reduction of CO2 to CO; the Faradaic efficiency (FE) reaches 94.1 % at -0.6 V vs. reversible hydrogen electrode (RHE).

Growing attention has been paid to nanoclusters with face-centered cubic (fcc) metal kernels, due to its structural similarity to bulk metals. We demonstrate that the use of tetradentate formamidinate ligands facilitate the construction of two fcc silver nanoclusters: [Ag

The first linear silver supercluster based on icosahedral Ag13 units has been constructed via bridging of dpa ligands: Ag61(dpa)27(SbF6)4 (Hdpa = dipyridylamine) (Ag61). Single-crystal X-ray diffraction reveals that this rod-shaped cluster consists of four vertex-sharing Ag13 icosahedra in a linear arrangement. This Ag61 cluster represents the longest one-dimensional metal nanocluster with a resolved structure. Unprecedented electron coupling develops between their constituent Ag13 units. Theoretical studies disclose that the stabilities of the two superclusters are dictated by a strong interaction between the Ag13 units as well as the ligand effect of the dpa-Ag motifs. The quantum size effect accounts for the significant enhancement of the metal-related absorptions and the red shift at the near-infrared region as the length of the cluster increases. This work sheds light on the evolution of one-dimensional materials and an understanding of the electronic communication between the constituent clusters.

The first all-amidinate-protected gold nanocluster [Au28 (Ph-form)12 ](OTf)2 (Ph-form=N,N'-diphenylformamidinate) (Au28 ) has been synthesized and structurally resolved. Single crystal X-ray diffraction reveals that Au28 has a compact Au4 @Au24 tetrahedral core-shell structure of T symmetry, which is fully protected by 12 bridging formamidinate ligands. This cluster is quite robust as indicated by the fact that it can stay intact in solution at 80 °C for 6 d. It exhibits excellent catalytic performance for the electroreduction of CO2 with 96.5 % Faradaic efficiency (FE) at -0.57 V and a maximum TOF of 1731 h-1 at -0.87 V. Its superior stability is also manifested in the fact that the supported catalyst Au28 /CNTs maintains stable potentials at ca. -0.69 V for 40 h with FE(CO)s>91 %. A superatomic electron configuration of 1S2 1P6 2S2 1D4 has been clarified by DFT computations, and the strong gold-ligand binding and geometric shell closure account for the superior stability of Au28 .

High yield and large scale synthesis are highly demanded for the studies of gold nanoclusters. We developed a "cluster from cluster" approach to assemble gold nanoclusters with preformed atomically precise Au 13 precursors. This facile approach has proved to be very effective in the synthesis of the well-known magic cluster [Au 25 (SR) 18 ] - , which could prepare the target cluster in high yield (overall yield up to ~100%) at large scale (gram-scale based on gold). This method can be applied in the synthesis of 10 Au 25 clusters with different R groups. This work presents an important approach that may be extended to high yield and large scale synthesis of other metal nanoclusters.

Identification of the authentic active species of cluster catalysis is rather challenging, and direct structural evidence is quite valuable and difficult to obtain. Two "isostructural" clusters, Ag

Silver nanoclusters containing Ag0 atoms protected by amino acids were synthesized and characterized. Chiral superatomic silver nanoclusters [Ag47 L12 (C≡Ct Bu)16 ]BF4 (L=l-/d-valine or l-/d-isoleucine) have been prepared by reducing AgC≡Ct Bu and amino acids (AAs) with NaBH4 . Single crystal X-ray diffraction revealed that these clusters have T symmetry, and the Ag47 metal kernel can be viewed as a tetracapped truncated tetrahedron (Ag17 ) surrounded with six W-shaped Ag5 units. The clusters are homochiral as evidenced by CD measurements. As for the strong CD signals, large contributions are found from the occupied Ag s,p states (superatomic D states) near the Fermi level. Electron counting revealed that these clusters are 18-electron systems, suggesting they are superatomic clusters. The superatomic nature with a 1S2 1P6 1D10 configuration was supported by DFT calculations. This work paves the way of taking AAs as facile chiral induction agents for the synthesis of metal nanoclusters.

Anions have been used to regulate the structures and luminescence of heterometallic clusters. Introducing ClO

Surface organic ligands are critical in dictating the structures and properties of atomically precise metal nanoclusters. In contrast to the conventionally used thiolate, phosphine and alkynyl ligands, nitrogen donor ligands have not been used in the protection for well-defined metal nanoclusters until recently. This review focuses on recent developments in atomically precise metal nanoclusters stabilized by different types of nitrogen donor ligands, in which the synthesis, total structure determination and various properties are covered. We hope that this review will provide insights into the rational design of N donor-protected metal nanoclusters in terms of structural and functional modulation.

Great attention has been paid to nanoclusters having face-centered-cubic (fcc) metal kernels, because of the similarity of metal packing to that of bulk gold. So far, there is no precedent example of an all-alkynyl-protected fcc gold nanocluster with more than 100 gold atoms. We report the synthesis and total structure determination of an alkynyl-protected gold nanocluster [NEt3H]2[Au110(p-CF3C6H4C≡C)48] (Au110). It has an fcc Au86 kernel with 24 peripheral Au(C≡CR)2 staples. The Au86 kernel consists of six close packing layers in the pattern of Au6:Au16:Au21:Au21:Au16:Au6. Electronic absorption spectroscopy shows Au110 has a molecular-like discrete electronic structure, and transient absorption experiments reveal its nonmetallic nature.

By directly reducing alkynyl-silver precursors, we successfully obtained a large alkynyl-protected silver nanocluster, (C7 H17 ClN)3 [Ag112 Cl6 (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 CH2 Cl2 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.

An alkynyl-protected gold nanocluster, Au22 (t BuC≡C)18 (1), has been synthesized and its structure has been determined by single-crystal X-ray diffraction. The molecular structure consists of a Au13 cuboctahedron kernel and three [Au3 (t BuC≡C)4 ] trimeric staples. The cluster 1 has strong luminescence in the solid state with a 15 % quantum yield, and it displays interesting thermochromic luminescence as revealed by temperature-dependent emission spectra. The enhanced room-temperature emission is characterized as thermally activated delayed fluorescence.

We report the controlled synthesis and structures of two isomeric gold nanoclusters, whose compositions are determined to be Au23(C≡CBut)15 (denoted as Au23-1 and Au23-2) by single-crystal X-ray di...

The identification of hydride(s) in gold nanoclusters is a challenging task, due to the instability of gold nanoclusters containing hydrides. Herein, we report two ultrastable hydrido gold nanoclusters protected by phosphine ligands: [Au20(PPh3)12H3](SbF6)3 (1H) and [Au20(PPh3)12H2(2-COOH-PhS)](PF6)3 (2H). The presence of hydrides in gold(0)-gold(i) nanoclusters is clearly demonstrated by ESI mass spectrometry and NMR spectroscopy. Single crystal structural determination reveals that both nanoclusters have an unprecedented Au20 core consisting of a Au9 unit and a Au11 unit. Such cores derived from the connection of different basic units are important for understanding the evolution and stability of metal nanoclusters. The hydride (H-) was also verified by a charge distribution calculation.

We report the structures, stability and catalysis properties of two Ag

Copper hydrides are important hydrogenation catalysts, but their poor stability hinders the practical applications. Ligand engineering is an effective strategy to tackle this issue. An amidinate ligand, N,N′-Di(5-trifluoromethyl-2-pyridyl)formamidinate (Tf-dpf) with four N-donors has been applied as a protecting agent in the synthesis of stable copper hydride clusters: Cu11H3(Tf-dpf)6(OAc)2 (Cu11) with three interfacial μ5-H and [Cu12H3(Tf-dpf)6(OAc)2]·OAc (Cu12) with three interstitial μ6-H. A solvent-triggered reversible interconversion between Cu11 and Cu12 has been observed thanks to the flexibility of Tf-dpf. Cu11 shows high activity in the reduction of 4-nitrophenol to 4-aminophenol, while Cu12 displays very low activity. Deuteration experiments prove that the type of hydride is the key in dictating the catalytic activity, for the interfacial μ5-H species in Cu11 are involved in the catalytic cycle whereas the interstitial μ6-H species in Cu12 are not. This work highlights the role of hydrides with regard to catalytic hydrogenation activity.

The boundary between molecular and metallic gold nanoclusters is of special interest. The difficulty in obtaining atomically precise nanoclusters larger than 2 nm limits the determination of such a boundary. The synthesis and total structural determination of the largest all-alkynyl-protected gold nanocluster (Ph

A Au

A golden fullerene Au32 cluster has been synthesized with amido and phosphine ligands as the protecting agents. Single-crystal X-ray structural analysis revealed that this gold nanocluster, [Au32 (Ph3 P)8 (dpa)6 ] (SbF6 )2 (Hdpa=2,2'-dipyridylamine), has a stable pseudo-Ih Au328+ core with S6 symmetry, which features an Au12 @Au20 Keplerate cage co-protected by Ph3 P and dpa ligands. Quantum-chemical studies were conducted to elucidate the origin of the special stability of this cluster, and suggest that it is electronically stabilized through metal-ligand interactions.

Destroying coordination open sites may significantly enhance the stability of metal nanoclusters., We report the synthesis and structures of two 34-atom metal nanoclusters, namely [Ag34(BTCA)3(C 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 1111111111111111111111111111111111 1111111111111111111111111111111111 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 1111111111111111111111111111111111 1111111111111111111111111111111111 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 1111111111111111111111111111111111 1111111111111111111111111111111111 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 CBut)9(tfa)4(CH3OH)3]SbF6 and [AuAg33(BTCA)3(C 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 1111111111111111111111111111111111 1111111111111111111111111111111111 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 1111111111111111111111111111111111 1111111111111111111111111111111111 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 1111111111111111111111111111111111 1111111111111111111111111111111111 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 CBut)9(tfa)4(CH3OH)3]SbF6, where H4BTCA is p-tert-butylthiacalix[4]arene and tfa is trifluoroacetate. Their compositions and structures have been determined by single-crystal X-ray structural analysis and ESI-MS. The cationic cluster consists of a centered icosahedron M@Ag12 (M = Ag or Au) core that is surrounded by 21 peripheral silver atoms. Surrounding protection is provided by four kinds of ligands, including three BTCA, nine tBuC 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 1111111111111111111111111111111111 1111111111111111111111111111111111 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 1111111111111111111111111111111111 1111111111111111111111111111111111 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 1111111111111111111111111111111111 1111111111111111111111111111111111 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 C, four tfa, and three methanol solvent ligands. It was found that the Ag5@BTCA μ5-coordination motif of thiacalixarene is critical for high stability of the title clusters, and extra stability enhancement can be achieved by doping a gold atom at the center of the silver cluster. This work suggests that coordination saturation should be taken into account in addition to electronic and geometric factors for analyzing metal nanocluster stabilities.

Two homoleptic alkynyl-protected gold clusters with compositions of Na[Au25 (C≡CAr)18 ] and (Ph4 P)[Au25 (C≡CAr)18 ] (Na⋅1 and Ph4 P⋅1, Ar=3,5-bis(trifluoromethyl)phenyl) were synthesized via a direct reduction method. 1 is a magic cluster analogous to [Au25 (SR)18 ]- in terms of electron counts and metal-to-ligand ratio. Single-crystal structure analysis reveals that 1 has an identical Au13 kernel to [Au25 (SR)18 ]- , but adopts a distinctly different arrangement of the six peripheral dimer staple motifs. The steric hindrance of alkynyl ligands is responsible for the D3 arrangement of Au25 . The introduction of alkynyl also significantly changes the optical absorption features of the nanocluster as supported by DFT calculations. This magic cluster confirms that there is a similar but quite different parallel alkynyl-protected metal cluster universe in comparison to the thiolated one.

We report the synthesis and crystal structure determination of two novel chiral gold nanoclusters. By utilizing BINAP, we isolate atomically precise intrinsically chiral Au nanoclusters [Au9(R-/S-BINAP)4](CF3COO)3 and [Au10(R-/S-BINAP)4(p-CF3C6H4C≡C)](CF3COO)3 in high yield with one-pot synthesis. Au9 has C2 geometry, while Au10 is C1 symmetric. Interestingly, reversible interconversion between Au9 and Au10 can be realized by the addition or removal of a RC≡CAu component. The transformation from Au9 to Au10 leads to significant enhancement of CD signals. The maximum anisotropy factor in the visible region of [Au10(BINAP)4(p-CF3C6H4C≡C)]3+ is the hitherto largest (up to 6.6 × 10–3) among gold nanoclusters, which is approximately twice of that of [Au9(BINAP)4]3+. This work demonstrates that the chiroptical activity of gold nanoclusters can be modulated by structural control through the introduction of second ligands.

We report a series of Ag-S nanoscale clusters in an attempt to understand the growth process of Ag2S clusters. UV-vis monitoring and crystallization at different stages of the reaction map out the cluster growth steps from Ag31S3(StBu)17(tfa)8(MeCN)4 (tfa = trifluoroacetate), to Ag45S7(StBu)24(tfa)7 to [Ag62S13(StBu)32(tfa)2](tfa)2, showing sequential eye-catching color changes. The cluster growth is associated with the in situ generation of S2-, which comes from the C-S bond cleavage of tert-butyl thiolate.

Gold clusters have attracted great interest for a long time, and homo and heterometallic gold clusters with hypercoordinated carbon are particularly interesting. This is due to their novel structures and intriguing physicochemical properties. In this review, recent results concerning homo and heterometallic gold(I) cluster compounds with hypercoordinated carbon are summarized, with emphasis on the rational design of phosphine ligands, synthesis of clusters, structure analysis, photophysical studies and their applications such as light emitters, cellular dyes and chirality sensors. We demonstrate that ligand modification, coordination of secondary metal ions and post-clustering functionalization are useful approaches in the preparation of carbon-centered homo and heterometallic gold clusters. The chemical stability of the cluster is enhanced through the binding between the hypercoordinated carbon and gold atoms. These gold clusters exhibit strong luminescence and are useful in cell imaging and chiral sensing. In addition, combine with ultrafast absorption experiments and quantum chemical calculations, the relationship between structures and properties of carbon-centered homo and heterometallic gold(I) clusters has been revealed.

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.

Hollow nanoclusters are intriguing for bridging the gap between small metal-organic cages and hollow nanoparticles and provide enormous opportunities for functional materials. Rational construction of hollow nanoclusters remains a challenge owing to the poor understanding of their formation pathways and difficulties in obtaining the intermediate structures. Here we report a catalyzed assembly strategy to construct hollow silver–sulfide clusters using a self-releasable carbonate template. The hollow Ag56 cluster and the carbonate-templated Ag33 intermediate are characterized by single-crystal X-ray analysis. Combining this data with a time-dependent UV-Vis spectroscopic investigation, we reveal the catalyst-like behavior of the self-releasable carbonate template and propose the corresponding mechanism. The assembly of hollow clusters using a self-releasable template may provide insight into understanding the formation mechanisms of other hollow nanoclusters and facilitate the design and construction of new hollow nanoclusters. The rational construction of hollow nanostructures is challenging owing to difficulties in elucidating formation pathways and observing intermediates. Here the authors probe the formation of the hollow Ag56 cluster and identify a catalyst-like self-releasing template formation mechanism.

The first all-amidinate-protected gold nanocluster [Au

Acetelyenediide (C22- ) species have been encapsulated in bimetallic and trimetallic clusters: [(AuL)6 Ag7 (C≡C)3 ](BF4 )7 (2) and [(AuL)6 AgCu6 (C≡C)3 ](BF4 )7 (3), L=phenylbis(2-pyridyl)phosphine (PPhpy2 ). Single-crystal X-ray diffraction analysis revealed that they are isostructural and six silver atoms in 2 are replaced with copper in 3. Both clusters have a trefoil skeleton, which can be viewed as three trigonal bipyramidal (LAu-C≡C-AuL)M2 Ag (M=Ag/Cu) motifs sharing a common silver atom. TDDFT calculations showed Cu-doping significantly increases the energy level of (C2 -Cu)-involved occupied orbital, thus inducing interesting transition coupling of dual-emission at low temperature. This work not only provides a strategy for constructing heterometallic clusters, but also shows the prospect for pursuing novel thermochromic luminescent materials by incorporating multi-congeneric metal components.

High-yield and large-scale synthesis are highly demanded for the studies of gold nanoclusters. We developed a "cluster from cluster" approach to assemble gold nanoclusters with preformed atomically precise Au

This work describes the synthesis and isolation of alkynyl/chloride-protected gold nanoclusters. Silica gel column chromatography works effectively in isolating gold nanoclusters from the as-synthesized cluster mixture to give three clusters Na[Au 25 L 18 ] ( Au 25 ), [HNEt 3 ] 3 [Au 67 L 32 Cl 4 ] ( Au 67 ), [HNEt 3 ] 4 [Au 106 L 40 Cl 12 ] ( Au 106 ), where L = 3,5-bis(trifluoromethyl)-phenylacetylide. Au 67 and Au 106 are new clusters and their total structures have been determined by X-ray single crystal diffraction. Au 67 contains a distorted Au 18 Marks decahedron shelled by an irregular Au 32 and further protected with two V-shaped Au 2 L 3 , 13 linear AuL 2 staples and four chlorides. Au 67 is the first structurally determined 34e superatomic gold nanocluster. Au 106 is composed of 106 Au atoms co-protected by alkynyls and chlorides. It has a Au 79 kernel, which is the same as that in Au 102 ( p -MBA) 44 . The surface structure of Au 106 includes 20 linear Au-alkynyl staples, five Cl-Au-Cl and two Cl-Au motifs. These three gold nanoclusters show size-dependent electrochemical properties. The combination of chloride and alkynyl pave a new path toward enriching structural diversity of gold nanoclusters.

Great attention has been paid to nanoclusters having face-centered-cubic (fcc) metal kernels, because of the similarity of metal packing to that of bulk gold. So far, there is no precedent example of an all-alkynyl-protected fcc gold nanocluster with more than 100 gold atoms. We report the synthesis and total structure determination of an alkynyl-protected gold nanocluster [NEt

Gold nanoclusters with surface open sites are crucial for practical applications in catalysis. We have developed a surface geometric mismatch strategy by using mixed ligands of different type of hindrance. When bulky phosphine Ph3 P and planar dipyridyl amine (Hdpa) are simultaneously used, steric repulsion between the ligands will reduce the ligand coverage of gold clusters. A well-defined access granted gold nanocluster [Au23 (Ph3 P)10 (dpa)2 Cl](SO3 CF3 )2 (Au23 , dpa=dipyridylamido) has been successfully synthesized. Single crystal structural determination reveals that Au23 has eight uncoordinated gold atoms in the shape of a distorted bicapped triangular prism. The accessibility of the exposed Au atoms has been confirmed quantitatively by luminescent titration with 2-naphthalenethiol. This cluster has excellent performance toward selective oxidation of benzyl alcohol to benzaldehyde and demonstrates excellent stability due to the protection of negatively charged multidentate ligand dpa.

We report two novel homoleptic alkynyl-protected gold nanoclusters, which were synthesized by direct reduction of AuC[triple bond, length as m-dash]CR. Single-crystal X-ray structural analysis reveals that they have compositions of Au42(C[triple bond, length as m-dash]CC6H4-2-CF3)22 (1) and Au50(C[triple bond, length as m-dash]C6H4-3-F)26 (2), respectively. Cluster 2 is the first Au50 nanocluster, and the metal-to-ligand ratios of 1 and 2 are different from those of known Aun(SR)m or Aux(C[triple bond, length as m-dash]CR)y nanoclusters. In addition, the metal kernels of these two clusters are built up unprecedented units. This work offers further insights into the synthesis of all-alkynyl-protected gold nanoclusters via a direct reduction method.

The syntheses and properties of two bimetallic nanoclusters [Au4 Ag23 (C≡CtBu)10 (dppf)4 Cl7 ](PF6 )2 and [Au5 Ag24 (C≡CC6 H4 -p-tBu)16 (dppf)4 Cl4 ](PF6 )3 are reported. The Au atoms distributed in both the cores and the surface motifs are clearly determined. The two nanoclusters show distinctly different geometric structures and electronic properties, which are attributed to the subtle changes in the surface alkynyl structures.

By directly reducing alkynyl-silver precursors, we successfully obtained a large alkynyl-protected silver nanocluster, (C

A series of enantiopure magnetic heterometallic coordination cubic cages [MII8CuII6L24(MeCN)12](ClO4)28 (1:M = Ni, 2:M = Co, L = chiral ditopic ligand) have been synthesized. These cages have cubic structures enclosing a 2250 A3 interior cavity with controllable chirality. Both the vertexes and the faces of the cubic cages are in chiral arrangements, which are dictated by the chiral amines used in forming the ligands. R-1-Phenylethylamine leads to 8Λ-6P configuration, while S-1-phenylethylamine results in 8Δ-6M ones. The magnetic behaviors of the cages are varied by the metals. They all show weak antiferromagnetic interaction. These cages represent the first series of enantiopure magnetic cubic cages, which offer a platform for the study of host–guest chemistry of potential chiral magnetic guests.