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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: [Ag52(5-F-dpf)16Cl4](SbF6)2(Ag52, 5-F-Hdpf = N,N′-di(5-fluoro-2-pyridinyl)formamidine) and [Ag53(5-Me-dpf)18](NO3)5(Ag53, 5-Me-Hdpf = N,N′-di(5-methyl-2-pyridinyl)formamidine). Single-crystal X-ray structural analysis revealed that the silver atoms in both clusters are in a layer-by-layer arrangement, which can be viewed as a portion of the fcc packing of silver. The nitrogen donors of amidinate ligands selectively passivate the {111} facets. All silver atoms are involved in the fcc packing, that is, no staple motifs are observed due to the linear arrangement of the four N donors of the dpf ligands. The characteristic optical absorption bands of Ag52and Ag53have been studied with a time-dependent density functional theory. This work provides a facile access to assembling atomically precise fcc-type nanoclusters and shows the prospect of amidinates as protecting ligands in synthesizing 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, Ag25Cu4Cl6(dppb)6(PhC≡C)12(SO3CF3)3(1) and Ag25Cu4Cl6H8(dppb)6(PhC≡C)12(SO3CF3)3(2H) (dppb is 1,4-bis(diphenylphosphine)butane), have been successfully isolated and structurally characterized. Both these clusters have a centered icosahedron Ag13core with the same peripheral composition and structure. The only difference is that 2Hhas eight hydrides but 1has none, that is, the kernels are Ag135+and Ag13H85+in 1and 2H, respectively. The catalytic reduction of 4-nitrophenol (4-NP) to 4-aminophenol (4-AP) as a model reaction is assessed with the two clusters. Cluster 2His very active with 100% yield within 2 h, whereas 1shows a very low conversion (∼8%) under the same conditions. Interestingly, high catalytic activity was observed when 1was converted to 2Hwith the oxidation of H2O2under catalytic conditions. The unprecedented transformation of a reduced nanocluster to an Ag(I)Cu(I) bimetallic cluster compound provides an excellent platform to determine the real active cluster in terms of metal cluster catalysis. The present work presents clear structural evidence that the catalytic performance of metal nanoclusters can be modulated by properly regulating the oxidation state of their constituted metal atoms.

An atomically resolved gold nanocluster Au99(C≡CC6H3-2,4-F2)40(Au99) with an unusual 59 valence electrons has been synthesized. Single-crystal X-ray diffraction reveals that its Au79kernel is a Au49Marks decahedron capped by two Au15units. The surface structure of Au99consists of 20 linear Au(C≡CR)2staples. Intercluster interactions are observed between these D5symmetric clusters. The existence of an unpaired electron is verified by magnetic measurement. Interestingly, this open-shell gold cluster Au99stays intact in toluene solution at 80 °C for more than a week, and it has good charging–discharging capability under electrochemical conditions. The compact ligand shell protection around the symmetric core accounts for the high stability. This work suggests that geometric factors may play a crucial role in determining the stability of a metal nanocluster, even though the cluster has an open-shell electronic structure.

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 (Ph4P)6[Au156(C≡CR)60] (R = 4-CF3C6H4-) (Au156) are reported. It presents an ideal platform for studying the relationship between the structure and the metallic nature. Au156has a rod shape with the length and width of the kernel being 2.38 and 2.04 nm, respectively. The cluster contains a concentric Au126core structure (Au46@Au50@Au30) protected by 30 linear RC≡C–Au–C≡CR staple motifs. It is interesting that Au156displays multiple excitonic peaks in the steady-state absorption spectrum (molecular) and pump-power-dependent excited-state dynamics as revealed in the transient absorption spectrum (metallic), which indicates that Au156is a critical crossover cluster for the transition from molecular to metallic state. Au156is the smallest-sized gold nanocluster showing metal-like electron dynamics, and it is recognized that the cluster shape is one of the important factors determining the molecular or metallic nature of a gold nanocluster.

The first linear silver supercluster based on icosahedral Ag13units 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 Ag13icosahedra in a linear arrangement. This Ag61cluster represents the longest one-dimensional metal nanocluster with a resolved structure. Unprecedented electron coupling develops between their constituent Ag13units. Theoretical studies disclose that the stabilities of the two superclusters are dictated by a strong interaction between the Ag13units 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.

Tailoring the surface ligands of metal nanoclusters is important for engineering unique configurations of metal nanoclusters. Thiacalix[4]arene has found extensive applications in the construction of metal nanoclusters. In this investigation, we present the synthesis and characterization of the first all-calixarene-protected silver nanoclusters, [Ag(CH3CN)4]2[Ag44(BTCA)6] (Ag44, H4BTCA = p-tert-butylthiacalix[4]arene). Single-crystal X-ray structural analysis reveals that all silver atoms are in a face-centered cubic (fcc) arrangement. The formation of such an fccstructure is attributed to the selectively passivation on {100} facets by BTCA4–. Thiacalixarene substantially facilitates the stability of Ag44due to its multiple coordination sites and bulkiness. Mass spectrometry and theoretical calculations reveal that Ag44is a superatomic silver nanocluster with 22 free electrons in the following configuration: 1S21P61D61F22S21D4. This work not only elucidates the impact of macrocyclic ligands on the stabilization of silver clusters but also furnishes an approach for assembling atomically precise fccnanoclusters.

Unprecedented geminal tetraauration of acetonitrile has been realized through C–H activation by Au(I)–Ag(I) clusters under mild conditions. The reaction of [OAu3Ag(dppy)3](BF4)2(dppy = diphenylphosphino-2-pyridine) (1), AgBF4, and acetonitrile in the presence of methanol at room temperature resulted in the isolation of the novel cluster [(CCN)2Au8Ag4(dppy)8(CH3CN)2](BF4)6(2). The centrosymmetric structure consists of two Au4Ag2motifs stabilized by hemilabile phosphines. Triply deprotonated acetonitrile (CCN3–) is found in a Au4Ag environment with the terminal carbon bridging four Au(I) centers and the nitrogen donor linking a Ag(I) ion, which is the first example of a μ5-CCN3–coordination mode. A concerted metalation/deprotonation process for the C–H activation of acetonitrile that indicates the importance of the oxo ion of the oxonium Au(I) cluster is proposed. Cluster 2emits bright green light in the solid state at room temperature upon UV irradiation.

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 Au86kernel with 24 peripheral Au(C≡CR)2staples. The Au86kernel consists of six close packing layers in the pattern of Au6:Au16:Au21:Au21:Au16:Au6. Electronic absorption spectroscopy shows Au110has a molecular-like discrete electronic structure, and transient absorption experiments reveal its nonmetallic nature.

We report the controlled synthesis and structures of two isomeric gold nanoclusters, whose compositions are determined to be Au23(C≡CBut)15(denoted as Au23-1and Au23-2) by single-crystal X-ray diffraction and matrix-assisted laser desorption ionization time-of-flight mass spectrometry. This is the first time isomerism is discovered in alkynyl-protected gold nanoclusters. The metal-to-ligand ratios in these two clusters are different from known Aun(SR)msystems and have not been observed in the Aux(C≡CPh)yfamily. This pair of isomers exhibits different optical properties, although they have similar structures and identical components. For both Au23clusters, time-dependent density functional theory calculations revealed the frontier orbitals highest occupied molecular orbital (HOMO)–1, HOMO, and lowest unoccupied molecular orbital (LUMO) are mainly constructed from the Au15kernel and V-shaped alkynyl–gold motifs. The HOMO → LUMO transition of Au23-1is optically forbidden, whereas it is allowed in Au23-2. It is also found that Au23-2cluster can be transformed to Au23-1spontaneously under ambient conditions. This work offers further insight into the synthesis and isomerism of all-alkynyl-protected gold nanoclusters and will stimulate more investigation of isomeric metal nanoclusters.

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)3and [Au10(R-/S-BINAP)4(p-CF3C6H4C≡C)](CF3COO)3in high yield with one-pot synthesis. Au9has C2geometry, while Au10is C1symmetric. Interestingly, reversible interconversion between Au9and Au10can be realized by the addition or removal of a RC≡CAu component. The transformation from Au9to Au10leads 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.

The past decades have witnessed great advances in the synthesis, structure determination, and properties investigation of coinage metal nanoclusters. These monodisperse clusters have well-defined molecular structures, which is advantageous in correlating structures and properties. Metal nanoclusters are large molecules consisting of many components, so it is a big challenge to prepare them in a rational way. Strenuous efforts have been made to control their geometric and electronic structures, in order to optimize their various properties.

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 Å3interior 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-6Pconfiguration, while S-1-phenylethylamine results in 8Δ-6Mones. 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.

Chiral metal nanoclusters have recently been attracting great attention. It is challenging to realize asymmetric catalysis via atomically precise metal nanoclusters. Herein, we report the synthesis and total structure determination of chiral clusters [Au7Ag8(dppf)3(l-/d-proline)6](BF4)2(l-/d-Au7Ag8). Superatomic clusters l-/d-Au7Ag8display intense and mirror-image Cotton effects in their CD spectra. Density functional theory (DFT) calculations were carried out to understand the correlation between electronic structures and the optical activity of the enantiomeric pair. Surprisingly, the incorporation of proline in a metal nanocluster can significantly promote the catalytic efficiency in asymmetric Aldol reactions. The increase of catalytic activity of Au7Ag8in comparison with organocatalysis by proline is attributed to the cooperative effect of the metal core and prolines, showing the advantages of the integration of metal catalysis and organocatalysis in a metal nanocluster.

Polynuclear Au(I) complexes continues to attract considerable attention because of their bright emissions in the visible wavelength, which hold promise in applications in luminescence, fluorescence sensing, and bioimaging. Despite various spectroscopic investigations on their steady state properties, detailed understanding of the origin of their emissions and excited state relaxations is still lacking. Here, we report femtosecond time-resolved transient absorption experiments combined with quantum chemical calculations on a brightly emissive [Au6Ag2(C)(dppy)6](BF4)4cluster in different solvents. Global analysis on the transient absorption spectra based on a sequential model gives three spectral components: (1) excited state absorption (ESA) of 1MLCTAustate (τ = 1–3 ps); (2) ESA of 3MLCTAustate (τ = 11–40 ps), and (3) ESA of 3MLCTAgstate (long-lived). By variation of the solvent’s polarity and hydrogen bonding ability, the relative population of the triplet MLCT states and the emission properties can be modulated. Especially in methanol, an additional site specific O–H···π bond is formed between methanol molecules and aromatic rings of ligands, which enhances the ultrafast nonradiative decay from the hydrogen bond stabilized 3MLCTAustate and reduces the population of the emissive 3MLCTAgstate. The results presented here about the excited state dynamics of luminescent gold(I)–silver(I) cluster allow a deeper insight into the origin of their emissions by monitoring the population of the emissive 3MLCTAgstate and dark 3MLCTAustate in different environments.

The environmental quality evaluation of seawater is a multicomponent and multi-factorial one, the water environment quality classification standards and the level of water pollution and so on are some vague concepts .Currently available evaluation models of water quality have more or less some shortage, Based on the variable fuzzy theory, the paper is to establish the variable fuzzy evaluation model of seawater quality and apply the approach to the comprehensive evaluation of Jiaozhou Bay seawater quality. The practice indicates that the model is simple, and can reasonably determine the sample's the relative membership degree and the relative membership functions to the different index standard ranges and be able to properly rate the sample by taking the stable result as the result of the comprehensive evaluation of seawater quality through changing the model and its parameters (a and p parameters change, change for four models, including a linear, three nonlinear) thereby providing a new approach and method for multi-objective comprehensive evaluation and decision-making in marine environmental field

A 64-nuclearity silver cluster encapsulating a unique POM anion [MnIIIMnIV2Mo14O56]17–has been synthesized. The formation of the templating core performs a reassembly process for increasing nuclearities from {MnMo9} to {Mn3Mo14}. It represents a rare inorganic meso anion containing mixed-valent Mn that is built up by d-{MnIVMo7} and l-{MnIVMo7} units connecting together through a {MnIII} fragment.

Ten polymeric silver(I) double salts containing embedded acetylenediide: [(Ag2C2)2(AgCF3CO2)9(L1)3] (1), [(Ag2C2)2(AgCF3CO2)10(L2)3]⋅H2O (2), [(Ag2C2)(AgCF3CO2)4(L3)(H2O)]⋅0.75 H2O (3), [(Ag2C2)1.5(AgCF3CO2)7(L4)2] (4), [(Ag2C2)(AgCF3CO2)7(L5)2(H2O)] (5), [(Ag2C2) (AgC2F5CO2)7(L1)3(H2O)] (6), [(Ag2C2)(AgCF3CO2)7(L1)3(H2O)]⋅2 H2O (7), [(Ag2C2)(AgC2F5CO2)6(L3)2] (8), [(Ag2C2)2(AgC2F5CO2)12(L4)2(H2O)4]⋅H2O (9), and [(Ag2C2)(AgCF3CO2)6(L3)2(H2O)]⋅H2O (10) have been isolated by varying the types of betaines, the perfluorocarboxylate ligands employed, and the reaction conditions. Single‐crystal X‐ray analysis has shown that 1–4all have a columnar structure composed of fused silver(I) double cages, with C22−species embedded in its stem and an exterior coat comprising anionic and zwitterionic carboxylates. For 5and 6, single silver(I) cages are linked into a beaded chain through both types of carboxylate ligands. In 7, two different coordination modes of L1connect the silver(I) polyhedra into a chain. For 8, the μ2‐O,O′ coordination mode of L3connects the silver(I) double cages into a chain. Compound 9exhibits a two‐dimensional architecture generated from the cross‐linkage of double cages by C2F5CO2−, L4, and [Ag2(C2F5CO2)2] units. Similar to 9, 10is also a two‐dimensional structure, which is formed by connecting the chains of linked double cages through [Ag2(CF3CO2)2] bridging.

The X-ray crystal structures of 1,1-di(p-methylphenyl)-2,2-dinitroethylene (2), 1,1-di(p-methoxylphenyl)-2,2-dinitroethylene (3), 1,1-di(p-fluorophenyl)-2,2- dinitroethylene (4), 1,1-di(p-chlorophenyl)-2,2-dinitroethylene (5), and 1-phenyl-1- (p-nitrophenyl)-2,2-dinitroethylene (6) are reported and compared with that of 1,1-diphenyl-2,2-dinitroethylene (1). Owing to steric repulsion between the aryl rings, the single bond lengths between C(1) and the two ring carbons atoms are longer than the normal sp2–sp2bond distance of 1.46 Å. For 4–6in which the aryl rings contain electron-withdrawing substituents (F, Cl, NO2), the double bonds between C(1) and C(2) are shorter than those in 2and 3, whose aryl rings containing electron-donating substituents. Furthermore, the steric repulsion between the aryl rings and C $$---$$ NO2fragments results in an appreciable twist about the central double bond. The two aryl rings of compounds 1–6make dihedral angles of 77.7, 66.6, 62.8, 80.9, 82.0, and 71.2°, and the two C $$---$$ NO2fragments make dihedral angles of 68.5, 67.8, 65.9, 76.9, 73.0, and 71.9°, respectively.

Five silver(I) double salts containing embedded acetylenediide, [Ag([12]crown-4)2][Ag10(C2)(CF3CO2)9([12]crown-4)2(H2O)3]·H2O (2), [Ag2C2·5 AgCF3CO2·(benzo[15]crown-5)·2 H2O]·0.5 H2O (3), [Ag4([18]crown-6)4(H2O)3][Ag18(C2)3(CF3CO2)16(H2O)2.5]·2.5 H2O (4), [Ag2C2·6 AgC2F5CO2·2([15]crown-5)]2 (5), and [(Ag2C2)2·(AgC2F5CO2)9·([18]crown-6)2·(H2O)3.5]·H2O (6), have been isolated by varying the types of crown ethers and anions employed. Single-crystal X-ray analysis has shown that complex 2 is composed of winding anionic chains with sandwiched [Ag([12]crown-4)2]⁺ ions accommodated in the concave cavities between them. In 3, silver(I) double cages each sandwiched by a couple of benzo[15]crown-5 ligands are linked by {Ag2(CF3CO2)2} bridges to form a one-dimensional structure. For 4, an anionic silver column is generated through fusion of two kinds of silver polyhedra (triangulated dodecahedron and bicapped trigonal antiprism), and the charge balance is provided by aqua-ligated [Ag([18]crown-6)]⁺ ions. Complex 5 is a centrosymmetric hexadecanuclear supermolecule composed of two [(η⁵-[15]crown-5)2(C2@Ag7)(μ-C2F5CO2)5] moieties connected through a {Ag2(C2F5CO2)2} bridge. Compound 6 is a discrete supermolecule containing an asymmetric (C2)2@Ag13 cluster core capped by two [18]crown-6 ligands in μ3-η⁵ and μ4-η⁶ ligation modes.

Five silver(I) double salts containing embedded acetylenediide, [Ag([12]crown‐4)2][Ag10(C2)(CF3CO2)9([12]crown‐4)2(H2O)3]⋅H2O (2), [Ag2C2⋅5 AgCF3CO2⋅(benzo[15]crown‐5)⋅2 H2O]⋅0.5 H2O (3), [Ag4([18]crown‐6)4(H2O)3][Ag18(C2)3(CF3CO2)16(H2O)2.5]⋅2.5 H2O (4), [Ag2C2⋅6 AgC2F5CO2⋅2([15]crown‐5)]2(5), and [(Ag2C2)2⋅(AgC2F5CO2)9⋅([18]crown‐6)2⋅(H2O)3.5]⋅H2O (6), have been isolated by varying the types of crown ethers and anions employed. Single‐crystal X‐ray analysis has shown that complex 2is composed of winding anionic chains with sandwiched [Ag([12]crown‐4)2]+ions accommodated in the concave cavities between them. In 3, silver(I) double cages each sandwiched by a couple of benzo[15]crown‐5 ligands are linked by {Ag2(CF3CO2)2} bridges to form a one‐dimensional structure. For 4, an anionic silver column is generated through fusion of two kinds of silver polyhedra (triangulated dodecahedron and bicapped trigonal antiprism), and the charge balance is provided by aqua‐ligated [Ag([18]crown‐6)]+ions. Complex 5is a centrosymmetric hexadecanuclear supermolecule composed of two [(η5‐[15]crown‐5)2(C2@Ag7)(μ‐C2F5CO2)5] moieties connected through a {Ag2(C2F5CO2)2} bridge. Compound 6is a discrete supermolecule containing an asymmetric (C2)2@Ag13cluster core capped by two [18]crown‐6 ligands in μ3‐η5and μ4‐η6ligation modes.

The new ligand 1,2-bis(4-pyridyl)ethane-N,N'-dioxide (L) was used to generate five lanthanide(iii) coordination networks of three structural types: (i) the isomorphous pair {[Ln(L)₃]·(ClO₄)₃·(H₂O)}_∞ (Ln = Er, 1; Yb, 2) comprises two interpenetrating α-polonium nets in which each lanthanide(iii) ion is in a rare homoleptic distorted octahedral coordination environment; (ii) an unprecedented mat-like pattern of three interwoven (6,3) nets is found in isomorphous {[Ln(NO₃)₃(L)_1.5]·H₂O}_∞ (Ln = Er, 3; Yb, 4); (iii) {[La(NO₃)₃(L) (CH₃OH)]· CH₃OH·CH₂Cl₂}_∞, 5, is built of an offset stacking of distorted square grids. The complex [Er(L')_0.5(H₂O)₃(C₂O₄)](ClO₄)·L'·6H₂O·(dioxane)_0.5 (L' = trans-1,2-bis(4-pyridyl)ethene-N,N'-dioxide), 6, is composed of (6,3) nets in which the Er(iii) ions are bridged by both L' ligands and oxalate ions.

The reactions of Ag2C2and the corresponding silver perfluoro-dicarboxylates result in the formation of three new double and triple salts, Ag2C2·3AgO2CCF2CF2CO2Ag·7H2O (1), 2Ag2C2·6AgO2CCF2CF2CO2Ag·AgNO3·12H2O (2) and Ag2C2·4AgO2CCF2CF2CF2CO2Ag·17.5H2O (3), which have been structurally characterized by single crystal X-ray analysis. Their structures contain silver cages of various shapes: crown in 1, pentagonal bipyramid together with monocapped pentagonal bipyramid in 2, and square antiprism in 3, each containing an encapsulated acetylide dianion. Except for the pentagonal bipyramid, the other three silver cages are unprecedented. Compound 2provides a unique example in which two kinds of silver polyhedra with different numbers of vertices (C2@Ag7and C2@Ag8) co-exist in the crystal structure.

The new silver(I) triple salt 2Ag2C2·AgF·9AgNO3·H2O was prepared by dissolving Ag2C2in an aqueous solution of AgNO3and AgBF4. Its crystal structure contains two kinds of monocapped trigonal prismatic C2@Ag7cages, with the capping atom occurring on one triangular face or one rectangular face.

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Silver nitrate reacts with sodium azide to give white powdery silver azide, which can be crystallized in aqueous ammonia. The compound belongs to orthorhombic space group Ibamwith a= 5.600(1), b= 5.980(6), c= 5.998(1) Å, and Z= 4. The layer-type structure is constructed from edge-sharing regular rectangles, each composed of silver atoms at its vertices with an enclosed azide anion in a tilted orientation. The linear and asymmetrical structure of the azide anion in crystalline silver azide has been confirmed by its Raman spectrum.

Rise of the silver surfer: A novel solution‐stable silver ethynediyl complex [Ag7(C2)(CF3CO2)5(bpy)5]⋅MeCN⋅0.5 MeOH (bpy=2,2′‐bipyridine) was prepared by reacting Me3SiCCH with [Ag(bpy)CF3CO2] in methanol (see figure). This complex represents the first example of a solution‐stable silver ethynediyl cluster, and it is yellow emissive in MeCN/MeOH at 77 K.

Nano‐Nuss: AgCCtBu reagiert mit AgOTf in Gegenwart eines Polyoxometallats (POM) als Templat unter Solvothermalbedingungen zu einem Kern‐Schale‐Nanocluster, dessen erdnussartige Struktur (siehe Bild) aus zwei Mo6O228−‐„Nüssen“ (grün) und einer Ag60‐Schale (lila) besteht. Nach elektrochemischen Untersuchungen wirkt die Silberschale als elektronisches Relais, und die POM‐Kerne stabilisieren als Redoxpuffer den Cluster.

The new triple salt (PhCH₂NMe₃)₄[Ag₁₇(C₂)₂(CF₃CO₂)₁₆(NO₃)(H₂O)₄] (1) features an asymmetric silver(i) double cage constructed from the edge-sharing of a triangulated dodecahedron and a monocapped square antiprism, and an anionic columnar structure is generated with an unprecedented μ₅-ligation mode of the nitrate ion.

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A new mixed-valent silver complex [AgII(tmc)][AgII(tmc)(H₂O)]₂·[AgI₁₁(C₂)(CF₃CO₂)₁₂(H₂O)₄]₂ (tmc = 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane) was synthesized by adding tmc to a concentrated aqueous solution of silver trifluoroacetate containing dissolved silver acetylide. Single-crystal X-ray analysis revealed that the resulting [AgII(tmc)]2+ and [AgII(tmc)(H₂O)]2+ complex cations induce the self-assembly of a centrosymmetric anionic cluster dimer from the Ag(I), C₂2− and CF₃CO₂− species. A new type of cluster core [C₂@Ag₈]Ag was observed, which takes the form of a bicapped trigonal prism with a pendant silver atom attached to one edge.

Unprecedented η3 π-donor behavior of the benzyltrimethylammonium ion is observed in the polymeric silver(i) complex [(PhCH₂NMe₃)Ag₇(C₂)(CF₃CO₂)₆]_n that comprises a columnar backbone constructed from the fusion of Ag₈ square antiprisms each enclosing an acetylide dianion.

9-Fluorenylidenemalononitrile reacts with 10-methyl-9,10-dihydroacridine in deaerated acetonitrile under irradiation with λ > 320 nm to give a coupling product 9-dicyanomethyl-9-(10'-methyl-9'-acridinyl)fluorene, characterized by X-ray crystallographic, MS and NMR analyses.

A novel luminescent acetylenediide-bridged tetranuclear copper(i) complex [Cu₄(μ-Ph₂Ppypz)₄(μ₄- η1,η2-C&z.tbd6;C)](ClO₄)₂ [Ph₂Ppypz = 2-(diphenylphosphino-6-pyrazol-1-yl)pyridine] has been synthesized and structurally characterized by X-ray crystallography.

In the mixed-valent complex [Ag^II(tmc)(BF₄)][Ag^I₆(C₂)(CF₃CO₂)₅(H₂O)]·H₂O, a [Ag^II(tmc)(BF₄)]⁺¹_∞ cationic column induces the assembly of a novel, anionic zigzag chain constructed from edge-sharing of silver(i) triangulated dodecahedra each enclosing a C₂²⁻ species.

The novel silver(i) triple salts AgCN·AgF·4AgCF₃CO₂·2L (L = MeCN or 2H₂O) exhibit the same type of layer structure, in which [F@Ag₆] units each representing a fluoride-centred octahedral silver cage are interconnected by μ₄-κC,κC∶κN,κN-cyanide and μ₄-O,O∶O',O'-trifluoroacetato bridges.

The novel coordination polymer [CuSCN(bpa)] [bpa = 1,2-bis(4-pyridyl)ethane] consists of two interpenetrating three-dimensional four-connected frameworks of rare 4²6³8 topology, each being constructed from the cross-linkage of infinite zigzag [(CuSCN)₂]_∞ chains by bpa ligands.

The novel coordination polymer [CuSCN(bpa)] [bpa = 1,2-bis(4-pyridyl)ethane] consists of two interpenetrating three-dimensional four-connected frameworks of rare 42638 topology, each being constructed from the cross-linkage of infinite zigzag [(CuSCN)2]∞ chains by bpa ligands.

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