Nestlike Silver(I) Thiolate Clusters with Tunable Emission Color Templated by Heteroanions

Four silver thiolate clusters, [H₃O][(Ag₃S₃)(BF₄)@Ag₂₇(tBuS)₁₈(hfac)₆H₂O] ⋅ H₂O ( 1 ; hfac = hexafluoroacetylacetone), [(Ag₃S₃)(CF₃CO₂)@Ag₃₀(tBuS)₁₆(CF₃CO₂)₉(CH₃CN)₄] ⋅ CF₃CO₂ ⋅ 4 CH₃CN ( 2 ), [(Ag₃S₃)(MoO₄)@Ag₃₀(tBuS)₁₆(CF₃CO₂)₉(CH₃CN)₄] ⋅ 2 CH₃CN ( 3 ), and [(Ag₃S₃)(CrO₄)@Ag₃₀(tBuS)₁₆(CF₃CO₂)₉(CH₃CN)₄] ⋅ 4 CH₃CN ( 4 ), were isolated. They have similar nestlike structures assembled by an [Ag₃S₃]³⁻ template together with one of the BF₄⁻, CF₃CO₂⁻, MoO₄²⁻, or CrO₄²⁻ anions. Interestingly, the solid-state emissions of 2 – 4 are dependent on the templating anions and are tunable from green to orange and then to red by changing the template from CF₃CO₂⁻ to MoO₄²⁻ and to CrO₄²⁻, and this may be correlated to the charge transfer between these templates to metal atoms. This work helps to understand the templating role of heteroanions and the relationship between structure and properties.     

Thermochromic Luminescent Nest‐Like Silver Thiolate Cluster

A novel discrete open high‐nuclearity nest‐like silver thiolate cluster complex, [Ag₃₃S₃(StBu)₁₆(CF₃COO)₉(NO₃)(CH₃CN)₂](NO₃) ( 1 ), has been isolated with nitrate and S^2? anions acting as structure‐directing templates. Its similar nest‐like structure has been assembled into an extended layer [Ag₃₁S₃(StBu)₁₆(NO₃)₉]_n ( 2 ) by adjustment of auxiliary ligand. More interestingly, both complexes exhibit temperature‐dependent luminescence of high sensitivity with a large fluorescence enhancement (12‐fold for 1 , 21‐fold for 2 ), which can be easily recognized by the naked‐eye (dramatic red‐shift Δ=104 nm for 1 , larger Δ=113 nm for 2 at 77 K compared to those at 298 K). The correlation between luminescent thermochromism and temperature‐dependent variation of the coordination modes of template NO₃^? anion, Ag???S and Ag???Ag distances are also elucidated through variable‐temperature single‐crystal X‐ray crystal structure (VT‐SCXRD) analyses.     

Silver Thiolate Nano‐sized Molecular Clusters and Their Supramolecular Covalent Frameworks: An Approach Toward Pre‐templated Synthesis

A series of seven new complexes including silver‐thiolate molecular clusters and their covalent supramolecular frameworks have been assembled from the silver carbide precursor Ag₂C₂ using a C₂²⁻ pre‐templated approach. Herein, two prototype clusters Ag₁₄(SR)₆ and CO₃@Ag_m (SR)₁₀ (R=isopropyl, cyclohexyl or tert ‐butyl; m= 18 or 20) are employed to construct cluster‐based metal–organic frameworks of different dimensions. In particular, both new ellipsoidal tetradecanuclear molecular cluster compounds, namely, Ag₁₄(S‐i Pr)₆(CO₂CF₃)₈⋅(DMSO)₆ (two polymorphic forms 1 , 2 ) and [Ag₁₄(S‐Cy)₆(CO₂CF₃)₈(DMSO)₄]⋅(DMSO)₃ ( 3 ), and a cluster‐based metal–organic framework {Ag₃[Ag₁₄(S‐i Pr)₆(CO₂CF₃)₁₁(H₂O)₃CH₃OH]⋅(H₂O)_2.5}_n ( 4 ) have been isolated and structurally characterized. Furthermore, increased acidity of the reaction mixture afforded three carboxylate‐templated cluster based frameworks: a chain‐like compound {[HN(CH₃)₂CO]⋅[CO₃@Ag₁₈(S‐t Bu)₁₀(NO₃)₇(DMF)₄]⋅DMF}_n ( 5 ), as well as two layer‐type compounds, namely, {Ag[CO₃@Ag₂₀(S‐i Pr)₁₀(CO₂CF₃)₉(CO₂HCF₃)(CH₃OH)₂]}_n ( 6 ) and {Ag₂[CO₃@Ag₂₀(S‐Cy)₁₀(CO₂CF₃)₁₀(CO₂HCF₃)₂(H₂O)₂]⋅(H₂O)₃⋅(CH₃OH)₃}_n ( 7 ) exhibiting sql ‐net characteristics. It is demonstrated that the C≡C²⁻ pre‐template, which draws several Ag⁺ ions together to form the C₂@Ag_n entity, plays an indispensable role in the syntheses of these compounds. Furthermore, covalent linkage of these nano‐sized silver thiolate clusters from one‐ to three‐dimensions revealed enormous potential for the future development of silver cluster‐based frameworks.     

Luminescence Regulation of Silver‐Thiolate Clusters Protected by 1,2‐Dithiolate‐o‐carborane

Engineering the surface of the metal clusters with the core structure maintained and tuning their luminescence in a wide range is still a challenge in the nanomaterial research. We modified six mono‐pyridyl ligands with different electronic effects (conjugation effect or induction effect) on a superatomic silver cluster [Ag₁₄(C₂B₁₀H₁₀S₂)₆(CH₃CN)₈] (denoted as Ag₁₄) through in situ site‐specific surface engineering, and obtained the corresponding clusters [Ag₁₄(C₂B₁₀H₁₀S₂)₆(CH₃CN)₆(L₁/L₂)₂] (denoted as NC‐1, 2, L₁/L₂ = 4‐acetylpyridine/ 4‐carboxypyridine) and [Ag₁₄(C₂B₁₀H₁₀S₂)₆(L₃/L₄/L₅/L₆)₈] (denoted as NC‐3, 4, 5, 6, L₃/L₄/L₅/L₆ = 4‐phenylpyridine/4‐(1‐naphthyl)pyridine/9‐(4‐pyridine)anthracene/9‐(4‐pyridine)pyrene). Through the modification of the Ag₁₄ cluster, a wide‐range luminescence from blue to red was realized. This work might provide a practical guide for improving the emission performance of metal clusters via surface engineering.     

Syntheses and characterization of dinuclear and tetranuclear AgI supramolecular complexes generated from symmetric and asymmetric molecular clips containing oxadiazole rings

A new asymmetric ligand, 5‐{3‐[5‐(4‐methylphenyl)‐1,3,4‐oxadiazol‐2‐yl]phenyl}‐2‐(pyridin‐3‐yl)‐1,3,4‐oxadiazole ( L5 ), which contains two oxadiazole rings, was synthesized and characterized. The assembly of symmetric 2,5‐bis(pyridin‐3‐yl)‐1,3,4‐oxadiazole ( L1 ) and asymmetric L5 with AgCO₂CF₃ in solution yielded two novel Ag^I complexes, namely catena‐poly[[di‐μ‐trifluoroacetato‐disilver(I)]‐bis[μ‐2,5‐bis(pyridin‐3‐yl)‐1,3,4‐oxadiazole]], [Ag₂(C₂F₃O₂)₂(C₁₂H₈N₄O)₂]_n or [Ag₂(μ₂‐O₂CCF₃)₂( L1 )₂]_n ( 1 ), and bis(μ₃‐5‐{3‐[5‐(4‐methylphenyl)‐1,3,4‐oxadiazol‐2‐yl]phenyl}‐2‐(pyridin‐3‐yl)‐1,3,4‐oxadiazole)tetra‐μ₃‐trifluoroacetato‐tetrasilver(I) dichloromethane monosolvate, [Ag₄(C₂F₃O₂)₄(C₂₂H₁₅N₅O₂)₂]·CH₂Cl₂ or [Ag₂(μ₃‐O₂CCF₃)₂( L5 )]₂·CH₂Cl₂ ( 2 ). Complex 1 displays a one‐dimensional ring–chain motif, where dinuclear Ag₂(CF₃CO₂)₂ units alternate with Ag₂( L1 )₂ macrocycles. This structure is different from previously reported Ag– L1 complexes with different anions. Complex 2 features a tetranuclear supramolecular macrocycle, in which each ligand adopts a tridentate coordination mode with the oxadiazole ring next to the p‐tolyl ring coordinated and that next to the pyridyl ring free. Two L5 ligands are bound to two Ag1 centres through two oxadiazole N and two pyridyl N atoms to form a macrocycle. The other two oxadiazole N atoms coordinate to the two Ag2 centres of the Ag₂(O₂CCF₃)₄ dimer. Each CF₃CO₂^? anion adopts a μ₃‐coordination mode, bridging the Ag1 and Ag2 centres to form a tetranuclear silver(I) complex. This study indicates that the donor ability of the bridging oxadiazole rings can be tuned by electron‐withdrawing and ‐donating substituents. The emission properties of ligands L1 and L5 and complexes 1 and 2 were also investigated in the solid state.     

Hydrothermal Synthesis,Structure, and Optical Properties of Two Nanosized Ln26@CO3 (Ln=Dy and Tb) Cluster‐Based Lanthanide–Transition‐Metal–Organic Frameworks (Ln MOFs)

Two Ln₂₆@CO₃ (Ln=Dy and Tb) cluster‐based lanthanide–transition‐metal–organic frameworks (Ln MOFs) formulated as [Dy₂₆Cu₃(Nic)₂₄(CH₃COO)₈(CO₃)₁₁(OH)₂₆(H₂O)₁₄]Cl ? 3 H₂O ( 1 ; HNic=nicotinic acid) and [Tb₂₆NaAg₃(Nic)₂₇(CH₃COO)₆(CO₃)₁₁(OH)₂₆Cl(H₂O)₁₅] ? 7.5 H₂O ( 2 ) have been successfully synthesized by hydrothermal methods and characterized by IR, thermogravimetric analysis (TGA), elemental analysis, and single X‐ray diffraction. Compound 1 crystallizes in the monoclinic space group Cc with a=35.775(12) Å, b=33.346(11) Å, c=24.424(8) Å, β=93.993(5)°, V=29065(16) ų, whereas 2 crystallizes in the triclinic space group P with a=20.4929(19) Å, b=24.671(2) Å, c=29.727(3) Å, α=81.9990(10)°, β=88.0830(10)°, γ=89.9940(10)°, V=14875(2) ų. Structural analysis indicates the framework of 1 is a 3D perovskite‐like structure constructed out of CO₃@Dy₂₆ building units and Cu⁺ centers by means of nicotinic acid ligand bridging. In 2 , however, nanosized CO₃@Tb₂₆ units and [Ag₃Cl]²⁺ centers are connected by Nic^? bridges to give rise to a 2D structure. It is worth mentioning that this kind of 4d–4f cluster‐based MOF is quite rare as most of the reported analogous compounds are 3d–4f ones. Additionally, the solid‐state emission spectra of pure compound 2 at room temperature suggest an efficient energy transfer from the ligand Nic^? to Tb³⁺ ions, which we called the “antenna effect”. Compound 2 shows a good two‐photon absorption (TPA) with a TPA coefficient of 0.06947 cm GM^?1 (1 GM=10^?50 cm⁴ s photon^?1), which indicates that compound 2 might be a good choice for third‐order nonlinear optical materials.     

A Three-dimensional Heteronuclear Polymer of [Ag2Fe（SCN）5（DMF）]n Containing Channels and One-dimensional Ag2S2-S-Ag2S2 Chains with Ag…Ag Interaction

Introduction So far, considerable attention has been paid to mag-netic interaction between two different metal ions.1-3 As a potential bridging ligand, thiocyanate can coordinate to a harder metal center with N atom and softer ones with S atom at the same time, resulting in the formation of small ferromagnetic coupling.2 On the other hand, the Fe(III) atom is a good candidate as a hard acid and Ag(I) is a good candidate as a soft acid, so that the Fe(III) centers could be expected to conn…     

Rate coefficients and mechanisms of the reaction of cl‐atoms with a series of unsaturated hydrocarbons under atmospheric conditions

Rate coefficients and/or mechanistic information are provided for the reaction of Cl‐atoms with a number of unsaturated species, including isoprene, methacrolein ( MACR ), methyl vinyl ketone ( MVK ), 1,3‐butadiene, trans‐2‐butene, and 1‐butene. The following Cl‐atom rate coefficients were obtained at 298 K near 1 atm total pressure: k(isoprene) = (4.3 ± 0.6) × 10^?10cm³ molecule^?1 s^?1 (independent of pressure from 6.2 to 760 Torr); k( MVK ) = (2.2 ± 0.3) × 10^?10 cm³ molecule^?1 s^?1; k( MACR ) = (2.4 ± 0.3) × 10^?10 cm³ molecule^?1 s^?1; k(trans‐2‐butene) = (4.0 ± 0.5) × 10^?10 cm³ molecule^?1 s^?1; k(1‐butene) = (3.0 ± 0.4) × 10^?10 cm³ molecule^?1 s^?1. Products observed in the Cl‐atom‐initiated oxidation of the unsaturated species at 298 K in 1 atm air are as follows (with % molar yields in parentheses): CH₂O (9.5 ± 1.0%), HCOCl (5.1 ± 0.7%), and 1‐chloro‐3‐methyl‐3‐buten‐2‐one (CMBO, not quantified) from isoprene; chloroacetaldehyde (75 ± 8%), CO₂ (58 ± 5%), CH₂O (47 ± 7%), CH₃OH (8%), HCOCl (7 ± 1%), and peracetic acid (6%) from MVK ; CO (52 ± 4%), chloroacetone (42 ± 5%), CO₂ (23 ± 2%), CH₂O (18 ± 2%), and HCOCl (5%) from MACR ; CH₂O (7 ± 1%), HCOCl (3%), acrolein (≈3%), and 4‐chlorocrotonaldehyde (CCA, not quantified) from 1,3‐butadiene; CH₃CHO (22 ± 3%), CO₂ (13 ± 2%), 3‐chloro‐2‐butanone (13 ± 4%), CH₂O (7.6 ± 1.1%), and CH₃OH (1.8 ± 0.6%) from trans‐2‐butene; and chloroacetaldehyde (20 ± 3%), CH₂O (7 ± 1%), CO₂ (4 ± 1%), and HCOCl (4 ± 1%) from 1‐butene. Product yields from both trans‐2‐butene and 1‐butene were found to be O₂‐dependent. In the case of trans‐2‐butene, the observed O₂‐dependence is the result of a competition between unimolecular decomposition of the CH₃CH(Cl)? CH(O?)? CH₃ radical and its reaction with O₂, with k_decomp/k_O2 = (1.6 ± 0.4) × 10¹⁹ molecule cm^?3. The activation energy for decomposition is estimated at 11.5 ± 1.5 kcal mol^?1. The variation of the product yields with O₂ in the case of 1‐butene results from similar competitive reaction pathways for the two β‐chlorobutoxy radicals involved in the oxidation, ClCH₂CH(O?)CH₂CH₃ and ?OCH₂CHClCH₂CH₃. © 2003 Wiley Periodicals, Inc. Int J Chem Kinet 35: 334–353, 2003     

Core Modulation of 70‐Nuclei Core‐Shell Silver Nanoclusters

The reaction of {(HNEt₃)₂[Ag₁₀(tBuC₆H₄S)₁₂]}_n, Ag₂O, Na₂MoO₄, and m‐methoxybenzoic acid (Hmbc) in CH₃OH/CH₂Cl₂ led to yellow crystals of [Ag₄S₄ (MoO₄)₅@Ag₆₆] (SD/Ag70b; SD=SunDi) only, while in the presence of DMF, additional dark‐red crystals of [Ag₁₀@ (MoO₄)₇@Ag₆₀] (SD/Ag70a) were obtained. SD/Ag70b consists of five MoO₄^2? ions wrapped by a shell of 66 Ag atoms, while SD/Ag70a contains a rare Ag₁₀ kernel consisting of five tetrahedra sharing faces and edges, surrounded by seven MoO₄^2? ions enclosed in a shell of 60 Ag atoms. The formation of the Ag₁₀ kernel originates from a reduction reaction during the self‐assembly process that involves DMF. This work provides the structural information of a unique Ag₁₀ kernel (five fused Ag₄ tetrahedra) and paves an avenue to trap elusive silver species with hierarchical multi‐shell silver nanocluster assemblies with the help of anion templates.     

Co3(HCOO)6 microporous metal-organic framework membrane for separation of CO2/CH4 mixtures

Continuous metal–organic framework‐type Co₃(HCOO)₆ intergrown films with a one‐dimensional zigzag channel system and pore aperture of 5.5 Å are prepared by secondary growth on preseeded macroporous glass‐frit disks and silicon wafers. The adsorption behavior of CO₂ or CH₄ single gases on the Co₃(HCOO)₆ membrane is investigated by in situ IR spectroscopy. It is shown that the isosteric heats of adsorption for CO₂ (17.7 kJ mol^?1) and CH₄ (14.4 kJ mol^?1) do not vary with increasing amount of adsorbed gases. The higher value of isosteric heat for CO₂ is an indication of the stronger interaction between the CO₂ and the Co₃(HCOO)₆ membrane. The Co₃(HCOO)₆ membrane is studied by binary gas permeation of CO₂ and CH₄ at different temperatures (0, 25, and 60 °C). The membrane has CO₂/CH₄ selectivity with a separation factor higher than 10, which is due to the unique structure and molecular sieving effect. Upon increasing the temperature from 0 to 60 °C, the preferred permeance of CO₂ over CH₄ is increased from 1.70×10^?6 to 2.09×10^?6 mol m^?2 s^?1 Pa^?1, while the separation factor for CO₂/CH₄ shows a corresponding decrease from 15.95 to 10.37. The effective pore size of the Co₃(HCOO)₆ material combined with the pore shape do not allow the two molecules to pass simultaneously, and once the CO₂ molecules are diffused in the micropores, the CH₄ is blocked. The supported Co₃(HCOO)₆ membrane retains high mechanical stability after a number of thermal cycles.     

Silver(I) Double and Multiple Salts Containing the 1,3‐Butadiynediide Dianion: Coordination Diversity and Assembly with the Supramolecular Synthon Ag4⊂CC?CC⊃Ag4

A series of 13 silver(I) double and multiple salts containing 1,3‐butadiynediide, C₄^2?, were synthesized by dissolving the silver carbide Ag₂C₄ in a concentrated aqueous solution of one or more of the silver salts AgNO₃, AgCF₃CO₂, AgC₂F₅CO₂, AgF, AgBF₄, and AgPF₆. The 1,3‐butadiynediide anion invariably adopts a μ₄,μ₄ coordination mode in these compounds, which indicates that the Ag₄?C?C? C?C?Ag₄ moiety can be used as a new type of metalloligand supramolecular synthon for the construction of coordination networks. Fine‐tuning with various ancillary anionic ligands caused the Ag₄ aggregate at each ethynide terminus to adopt a butterfly‐shaped, planar, or barblike configuration, within which the silver–ethynide interactions can be classified into three types: σ, π, and mixed (σ,π). The effect of coexisting nitrile ligands and quaternary ammonium salts on supramolecular assembly with the above synthon was also explored. The hydrolysis of PF₆^? and BF₄^? led to the formation of the quadruple salt Ag₂C₄?4 AgNO₃?AgPF₂O₂?Ag₃PO₄ and a novel (F)₂(H₂O)₁₈ hydrogen‐bonded tape in the triple salt Ag₂C₄?2 AgF? 10 AgC₂F₅CO₂?CH₃CN?12 H₂O, respectively. The largest silver–ethynide cluster aggregate described to date, (C₄)₃@Ag₁₈, occurs in 3 Ag₂C₄? 12 AgC₂F₅CO₂?5[(BnMe₃N)C₂F₅CO₂]? 4 H₂O (Bn=benzyl).     

Synthesis,structure, magnetic properties and kinetics of formation of a cluster containing a {Cu3(μ3-OH)} core supported by a triazole-based ligand

The trinuclear copper complex, [Cu₃(μ₃-OH)(CTMB)₃(NO₃)₂(CH₃CN)₂]·5CH₃CN·H₂O (1) {CTMB = cyclohexotriazole-3-(4-methoxybenzamide)}, has been prepared by mixing Cu(NO₃)₂·2.5H₂O and CHMBH {CHMBH = N,N′-cyclohexane-1,2-diylidene-bis(4-methoxybenzoylhydrazide)} in acetonitrile under ambient conditions. Compound 1 was characterized by IR and UV–visible spectroscopies as well as elemental analyses. X-ray crystallography shows that the cluster contains a {Cu₃(μ₃-OH)} core supported by three triazole-based Schiff base ligands. Each Cu is bound to the 2-N of one triazole ring and the 1-N of another. However, the coordination sphere of each Cu is different, one is five-coordinate and the other two are six-coordinate and bridged by a NO₃ group. The six-coordinate sites are different, one has a terminal NO₃ and the other a MeCN ligand. Magnetic measurements revealed the presence of isotropic and antisymmetric exchange between the copper(II) centers. The data were analyzed using the Hamiltonian containing isotropic exchange for an isosceles triangle together with antisymmetric exchange: H = –J₁(S₁S₂ + S₂S₃)?J₂S₁S₃ + G[S₁ × S₂ + S₂ × S₃ + S₃ × S₁]. Compound 1 exhibits strong antiferromagnetic coupling with J₁ = ?180 and J₂ = ?118 cm^?1 and antisymmetric exchange with G_z = 15 cm^?1. Stopped flow spectrophotometric studies show that the formation of 1 occurs in three distinct phases and the kinetics of each phase has been determined.     

Cations Controlling the Chiral Assembly of Luminescent Atomically Precise Copper(I) Clusters

Chiral assembly and asymmetric synthesis are critically important for the generation of chiral metal clusters with chiroptical activities. Here, a racemic mixture of [K(CH₃OH)₂(18‐crown‐6)]⁺[Cu₅(S^tBu)₆]^? ( 1?CH₃OH ) in the chiral space group was prepared, in which the chiral red‐emissive anionic [Cu₅(S^tBu)₆]^? cluster was arranged along a twofold screw axis. Interestingly, the release of the coordinated CH₃OH of the cationic units turned the chiral 1?CH₃OH crystal into a mesomeric crystal [K(18‐crown‐6)]⁺[Cu₅(S^tBu)₆]^? ( 1 ), which has a centrosymmetric space group, by adding symmetry elements of glide and mirror planes through both disordered [Cu₅(S^tBu)₆]^? units. The switchable chiral/achiral rearrangement of [Cu₅(S^tBu)₆]^? clusters along with the capture/release of CH₃OH were concomitant with an intense increase/decrease in luminescence. We also used cationic chiral amino alcohols to induce the chiral assembly of a pair of enantiomers, [d /l ‐valinol(18‐crown‐6)]⁺[Cu₅(S^tBu)₆]^? ( d /l ‐Cu_5V ), which display impressive circularly polarized luminescence (CPL) in contrast to the CPL‐silent racemic mixture of 1?CH₃OH and mesomeric 1 .     

A Cationic MOF with High Uptake and Selectivity for CO2 due to Multiple CO2‐Philic Sites

The reaction of N‐rich pyrazinyl triazolyl carboxyl ligand 3‐(4‐carboxylbenzene)‐5‐(2‐pyrazinyl)‐1H‐1,2,4‐triazole (H₂cbptz) with MnCl₂ afforded 3D cationic metal–organic framework (MOF) [Mn₂(Hcbptz)₂(Cl)(H₂O)]Cl ? DMF ? 0.5 CH₃CN ( 1 ), which has an unusual (3,4)‐connected 3,4T1 topology and 1D channels composed of cavities. MOF 1 has a very polar framework that contains exposed metal sites, uncoordinated N atoms, narrow channels, and Cl^? basic sites, which lead to not only high CO₂ uptake, but also remarkably selective adsorption of CO₂ over N₂ and CH₄ at 298–333 K. The multiple CO₂‐philic sites were identified by grand canonical Monte Carlo simulations. Moreover, 1 shows excellent stability in natural air environment. These advantages make 1 a very promising candidate in post‐combustion CO₂ capture, natural‐gas upgrading, and landfill gas‐purification processes.     

Synthesis and Reaction Chemistry of Sb(ECH2CH2NMe2)3 (E = O,S)

The antimony aminoalkoxide and aminothiolates Sb(ECH₂CH₂NMe₂)₃ [E = O ( 1 ), S ( 2 )] were synthesized and their ability to form adducts with other metal moieties investigated. Compound 1 forms 1:1 adducts with NiI₂ ( 3 ) and M(acac)₂ [M = Cd ( 4 ), Ni ( 5 )], while 2 undergoes ligand exchange with AlMe₃ to afford Me₂AlSCH₂CH₂NMe₂ ( 6 ). The structures of 2 – 4 and 6 were determined. Compound 2 incorporates three S, N‐chelating ligands though the interaction with nitrogen is weaker than in analogous alkoxide complexes. Product 3 reveals one iodine has migrated from nickel to antimony, and all three alkoxide ligands bridge the two metals through μ₂‐O atoms. In contrast, in 4 , only one alkoxide links the antimony and cadmium. Compound 6 adopts the same structure, a chelating S,N ligand generating a tetrahedral center at aluminum, as known tBu₂AlSCH₂CH₂NR₂ species (R = Me, Et).     

Structure‐Directing Forces in Intercluster Compounds of Cationic [Ag14(CCtBu)12Cl]+ Building Blocks and Polyoxometalates: Long‐Range versus Short‐Range Bonding Interactions

Crystallization of [Ag₁₄(C?CtBu)₁₂Cl][BF₄] and different polyoxometalates in organic solvents yields a series of new intercluster compounds: [Ag₁₄(C?CtBu)₁₂Cl(CH₃CN)]₂[W₆O₁₉] ( 1 ), (nBu₄N)[Ag₁₄(C?CtBu)₁₂Cl(CH₃CN)]₂[PW₁₂O₄₀] ( 2 ), and [Ag₁₄(C?CtBu)₁₂Cl]₂[Ag₁₄(C?CtBu)₁₂Cl(CH₃CN)]₂[SiMo₁₂O₄₀] ( 3 ). Applying the same technique to a system starting from polymeric {[Ag₃(C?CtBu)₂][BF₄]?0.6 H₂O}_n and the polyoxometalate (nBu₄N)₂[W₆O₁₉] results in the formation of [Ag₁₄(C?CtBu)₁₂(CH₃CN)₂][W₆O₁₉] ( 4 ). Here, the Ag₁₄ cluster is generated from polymeric {[Ag₃(C?CtBu)₂][BF₄]?0.6 H₂O}_n during crystallization. In a similar way, [Ag₁₅(C?CtBu)₁₂(CH₃CN)₅][PW₁₂O₄₀] ( 5 ) has been obtained from {[Ag₃(C?CtBu)₂][BF₄]?0.6 H₂O}_n and (nBu₄N)₃[PW₁₂O₄₀]. The use of charged building blocks was intentional, because at these conditions the contribution of long‐range Coulomb interactions would benefit most from full periodicity of the intercluster compound, thus favoring formation of well‐crystalline materials. The latter has been achieved, indeed. However, as a most conspicuous feature, equally charged species aggregate, which demonstrates that the short‐range interactions between the “surfaces” of the clusters represent the more powerful structure direction forces than the long‐range Coulomb bonding. This observation is of significant importance for understanding the mechanisms underlying self‐organization of monodisperse and structurally well‐defined particles of nanometer size.     

Neue Silber‐Tellurid Cluster stabilisiert mit zweizähnigen Phosphanen: Synthese und Struktur von {[Ag5(TePh)6(Ph2P(CH2)2PPh3)](Ph2P(CH2)2PPh2)}∞, [Ag18Te(TePh)15(Ph2P(CH2)3PPh2)3Cl] und [Ag38Te13(TetBu)12(Ph2P(CH2)2PPh2)3]

Novel Silver‐Telluride Clusters Stabilised with Bidentate Phosphine Ligands: Synthesis and Structure of {[Ag₅(TePh)₆(Ph₂P(CH₂)₂PPh₃)](Ph₂P(CH₂)₂PPh₂)}_∞, [Ag₁₈Te(TePh)₁₅(Ph₂P(CH₂)₃PPh₂)₃Cl], and [Ag₃₈Te₁₃(Te t Bu)₁₂(Ph₂P(CH₂)₂PPh₂)₃] Bidentate phosphine ligands have been found effective to stabilise polynuclear cores containing silver and chalcogenide ligands. They can act as intra and intermolecular bridges between the silver centres. The clusters {[Ag₅(TePh)₆(Ph₂P(CH₂)₂PPh₃)](Ph₂P(CH₂)₂PPh₂)}_∞ ( 1 ), [Ag₁₈Te(TePh)₁₅(Ph₂P(CH₂)₃PPh₂)₃Cl] ( 2 ), and [Ag₃₈Te₁₃(TetBu)₁₂(Ph₂P(CH₂)₂PPh₂)₃] ( 3 ) have been prepared and their molecular structure determined. Compound 2 and 3 are molecular structures with separated cluster cores while 1 forms a polymeric chain bridged by phosphine ligands. ( 1 : space group P2₁/c (No. 14), Z = 4, a = 3518,1(7) pm, b = 2260,6(5) pm, c = 3522,1(7) pm, β = 119,19(3)°; 2 : space group R3 (No. 148), Z = 6, a = b = 3059,4(4) pm, c = 5278,8(9) pm; 3: space group Pccn (No. 56), Z = 4, a = 3613,0(9) pm, b = 3608,6(7) pm, c = 2153,5(8) pm)     

Coordination Chemistry of Diiodine and Implications for the Oxidation Capacity of the Synergistic Ag+/X2 (X=Cl,Br, I) System

The synergistic Ag⁺/X₂ system (X=Cl, Br, I) is a very strong, but ill‐defined oxidant—more powerful than X₂ or Ag⁺ alone. Intermediates for its action may include [Ag_m(X₂)_n]^m+ complexes. Here, we report on an unexpectedly variable coordination chemistry of diiodine towards this direction: ( A )Ag‐I₂‐Ag( A ), [Ag₂(I₂)₄]²⁺( A ^?)₂ and [Ag₂(I₂)₆]²⁺( A ^?)₂?(I₂)_x≈0.65 form by reaction of Ag( A ) ( A =Al(OR^F)₄; R^F=C(CF₃)₃) with diiodine (single crystal/powder XRD, Raman spectra and quantum‐mechanical calculations). The molecular ( A )Ag‐I₂‐Ag( A ) is ideally set up to act as a 2 e^? oxidant with stoichiometric formation of 2 AgI and 2 A ^?. Preliminary reactivity tests proved this ( A )Ag‐I₂‐Ag( A ) starting material to oxidize n‐C₅H₁₂, C₃H₈, CH₂Cl₂, P₄ or S₈ at room temperature. A rough estimate of its electron affinity places it amongst very strong oxidizers like MF₆ (M=4d metals). This suggests that ( A )Ag‐I₂‐Ag( A ) will serve as an easily in bulk accessible, well‐defined, and very potent oxidant with multiple applications.     

A Functionalized Ag2S Molecular Architecture: Facile Assembly of the Atomically Precise Ferrocene‐Decorated Nanocluster [Ag74S19(dppp)6(fc(C{O}OCH2CH2S)2)18]

A ferrocene‐based dithiol 1,1′‐[fc(C{O}OCH₂CH₂SH)₂] has been prepared and treated with a Ag^I salt to form the stable dithiolate compound [fc(C{O}OCH₂CH₂SAg)₂]_n (fc=[Fe(η⁵‐C₅H₄)₂]). This is used as a reagent for the preparation of the nanocluster [Ag₇₄S₁₉(dppp)₆(fc(C{O}OCH₂CH₂S)₂)₁₈] which was obtained in good yield (dppp=1,3‐bis(diphenylphosphino)propane).