Fabrication of a family of atomically precise silver nanoclusters via dual-level kinetic control

The controllable preparation of metal nanoclusters in high yield is an essential prerequisite for their fundamental research and extensive application. Here a synthetic approach termed “dual-level kinetic control” was developed to fabricate a family of new silver nanoclusters. The introduction of secondary ligands was first exploited to retard the reduction rate and accomplish the first-level kinetic control. And the cooling of the reaction was performed to further slow the reduction down and accomplish the second-level kinetic control. A family of atomically precise silver nanoclusters (including [Ag₂₅(SR)₁₈]⁻, [Ag₃₄(SR)₁₈(DPPP)₃Cl₄]²⁺, [Ag₃₆(SR)₂₆S₄]²⁺, [Ag₃₇(SR)₂₅Cl₁]⁺, and [Ag₅₂(SR)₂₈Cl₄]²⁺) were controllably prepared and structurally determined. The developed “dual-level kinetic control” hopefully acts as a powerful synthetic tool to manufacture more nanoclusters with unprecedented compositions, structures, and properties.

A dual-level kinetic control was exploited to fabricate a family of atomically precise silver nanoclusters.     

Alternating Array Stacking of Ag26Au and Ag24Au Nanoclusters

An assembly strategy for metal nanoclusters using electrostatic interactions with weak interactions, such as C?H???π and π???π interactions in which cationic [Ag₂₆Au(2‐EBT)₁₈(PPh₃)₆]⁺ and anionic [Ag₂₄Au(2‐EBT)₁₈]^? nanoclusters gather and assemble in an unusual alternating array stacking structure is presented. [Ag₂₆Au(2‐EBT)₁₈(PPh₃)₆]⁺ [Ag₂₄Au(2‐EBT)₁₈]^? is a new compound type, a double nanocluster ion compound (DNIC). A single nanocluster ion compound (SNIC) [PPh₄]⁺ [Ag₂₄Au(2‐EBT)₁₈]^? was also synthesized, having a k‐vector‐differential crystallographic arrangement. [PPh₄]⁺ [Ag₂₄Au(2,4‐DMBT)₁₈]^? adopts a different assembly mode from both [Ag₂₆Au(2‐EBT)₁₈(PPh₃)₆]⁺ [Ag₂₄Au(2‐EBT)₁₈]^? and [PPh₄]⁺ [Ag₂₄Au(2‐EBT)₁₈]^?. Thus, the striking packing differences of [Ag₂₆Au(2‐EBT)₁₈(PPh₃)₆]⁺ [Ag₂₄Au(2‐EBT)₁₈]^?, [PPh₄]⁺ [Ag₂₄Au(2‐EBT)₁₈]^? and the existing [PPh₄]⁺ [Ag₂₄Au(2,4‐DMBT)₁₈]^? from each other indicate the notable influence of ligands and counterions on the self‐assembly of nanoclusters.     

New atomically precise M1Ag21 (M = Au/Ag) nanoclusters as excellent oxygen reduction reaction catalysts

By introducing 1,1′-bis-(diphenylphosphino)ferrocene (dppf) as an activating ligand, two novel nanoclusters, M1Ag21 (M = Au/Ag), have been controllably synthesized and structurally characterized. The atomically precise structures of the M1Ag21 nanoclusters were determined by SCXC and further confirmed by ESI-TOF-MS, TGA, XPS, DPV, and FT-IR measurements. The M1Ag21 nanoclusters supported on activated carbon (C) are exploited as efficient oxygen reduction reaction (ORR) catalysts in alkaline solutions. Density functional theory (DFT) calculations verify that the catalytic activities of the two cluster-based systems originate from the significant ensemble synergy effect between the M₁₃ kernel and dppf ligand in M1Ag21. This work sheds lights on the preparation of cluster-based electrocatalysts and other catalysts that are activated and modified by peripheral ligands.

The presence of 1,1′-bis-(diphenylphosphino)ferrocene ligands and ensemble effects in novel nanoclusters M₁Ag₂₁(dppf)₃(SAdm)₁₂ (M = Au/Ag) provide excellent ORR performances.     

Extraction of silver from water into nitrobenzene using sodium dicarbollylcobaltate in the presence of valinomycin

Summary From extraction experiments andg-activity measurements, the extraction constant corresponding to the Ag⁺(aq) + NaL⁺(nb)?AgL⁺(nb) + Na⁺(aq) equilibrium in the two-phase water-nitrobenzene system (L=valinomycin; aq=aqueous phase, nb=nitrobenzene phase) was evaluated as log K_ex(Ag⁺,NaL⁺)=-0.6±0.1. The stability constant of the valinomycin-silver complex in nitrobenzene saturated with water was calculated: log b_nb(AgL⁺)=4.6±0.1. The stability constants of complexes of some univalent cations with valinomycin were summarized and discussed.     

Polarographic and voltammetric investigations in N-methylpyrrolidinone(2) and N-methylthiopyrrolidinone(2)

Polarographic and voltammetric methods were employed to study the influence of N-methylpyrrolidinone(2) (NMP) and N-methylthiopyrrolidinone(2) (NMTP) towards a series of cations. In NMP reversible electrode reactions were observed for Na⁺, K⁺, Tl⁺, Zn²⁺, Cd²⁺, Cu²⁺, Ag⁺ and irreversible reductions for Ba²⁺, Mn²⁺, Co²⁺ and Ni²⁺. 0.1 mol l^?1 tetraethylammoniumperchlorate solutions served as supporting electrolytes. Li⁺ was not electroactive in the supporting electrolyte mentioned, but yielded an irreversible cathodic wave in tetra-n-butylammonium perchlorate. In NMTP, Li⁺, Na⁺, Tl⁺, Zn²⁺, Cd²⁺, Cu⁺ and Ag⁺ gave reversible cathodic waves on the DME, while Mn²⁺, Co²⁺ and Ni²⁺ were reduced in an irreversible electrode process. Bisbiphenylchromium iodide serving as a reference system throughout this study showed reversible behaviour in both solvents. A comparison of E_1/2 for given ions in both solvents showed a shift of about 0.5 V to more positive values in the case of a typically hard cation such as Na⁺ whereas soft cations such as Ag⁺ and Cu⁺ shifted by more than 0.8 V to more negative values. The effects of these two solvents on the cations studied is discussed in terms of donor acceptor interactions between the cation and the solvent molecules with special respect to the changes caused by replacing the oxygen atom in NMP by a sulphur atom.     

Ternäre Halogenide vom Typ A3MX6. II. Das System Ag3−xNaxYCl6: Synthese,Strukturen, Ionenleitfähigkeit

Ternary Halides of the A₃MX₆ Type. II. The System Ag_3?xNa_xYCl₆: Synthesis, Structures, Ionic Conductivity . The influence of the substitution of Ag⁺ by Na⁺ ions on the crystal structure and the ionic conductivity of Ag₃YCl₆ (stuffed LiSbF₆-type structure) has been investigated. The system Ag_3?xNa_xYCl₆ forms a complete solid solution. The stuffed LiSbF₆-type structure is stable for all compositions. For compounds with Na⁺ contents of x > 1.67, the cryolite-type structure is observed as the high-temperature form. The transition temperature decreases steadily with increasing Na⁺ content. The “end member” phase Na₃YCl₆ transforms at 243 K from the monoclinic cryolite-type structure to the stuffed LiSbF₆-type structure (trigonal, R3 ; a = 697.3(1), c = 1 868.4(14) pm, Z = 3; R = 0.094; R_w = 0.069). The crystal structures of Ag_1.3Na_1.7YCl₆ (trigonal, R3 ; a = 691.5(2), c = 1 853.7(6) pm, Z = 3; R = 0.099, R_w = 0.081) and AgNa₂YCl₆ (trigonal, R3 ; a = 691.7(1), c = 1 853.9(5) pm, Z = 3; R = 0.099, R_w = 0.064) have also been determined. Both chlorides crystallize like Ag₃YCl₆ and Na₃YCl₆-I in the stuffed LiSbF₆-type structure. The monovalent cations, Ag⁺ and Na⁺, are distributed over the five octahedral voids that are occupied by the Ag⁺ ions alone in Ag₃YCl₆. The ionic conductivity for compounds within the solid solution Ag_3?xNa_xYCl₆ decreases with increasing Na⁺ content. The values for Na₃YCl₆ (σ = 1 · 10^?6 Ω^?1 cm^?1 at T = 500 K) are by 2.5 to 3.5 orders of magnitude smaller than those for Ag₃YCl₆ (σ = 6 · 10^?4 Ω^?1 cm^?1 at T = 500 K).     

Crystallographic characterization of the metal–organic framework Fe2(bdp)3 upon reductive cation insertion

Precisely locating extra-framework cations in anionic metal–organic framework compounds remains a long-standing, yet crucial, challenge for elucidating structure–performance relationships in functional materials. Single-crystal X-ray diffraction is one of the most powerful approaches for this task, but single crystals of frameworks often degrade when subjected to post-synthetic metalation or reduction. Here, we demonstrate the growth of sizable single crystals of the robust metal–organic framework Fe₂(bdp)₃ (bdp²⁻ = benzene-1,4-dipyrazolate) and employ single-crystal-to-single-crystal chemical reductions to access the solvated framework materials A₂Fe₂(bdp)₃·yTHF (A = Li⁺, Na⁺, K⁺). X-ray diffraction analysis of the sodium and potassium congeners reveals that the cations are located near the center of the triangular framework channels and are stabilized by weak cation–π interactions with the framework ligands. Freeze-drying with benzene enables isolation of activated single crystals of Na_0.5Fe₂(bdp)₃ and Li₂Fe₂(bdp)₃ and the first structural characterization of activated metal–organic frameworks wherein extra-framework alkali metal cations are also structurally located. Comparison of the solvated and activated sodium-containing structures reveals that the cation positions differ in the two materials, likely due to cation migration that occurs upon solvent removal to maximize stabilizing cation–π interactions. Hydrogen adsorption data indicate that these cation–framework interactions are sufficient to diminish the effective cationic charge, leading to little or no enhancement in gas uptake relative to Fe₂(bdp)₃. In contrast, Mg_0.85Fe₂(bdp)₃ exhibits enhanced H₂ affinity and capacity over the non-reduced parent material. This observation shows that increasing the charge density of the pore-residing cation serves to compensate for charge dampening effects resulting from cation–framework interactions and thereby promotes stronger cation–H₂ interactions.

Single-crystal X-ray diffraction reveals structural influences on gas adsorption properties in anionic metal–organic frameworks.     

A Pseudorotaxane System Containing γ-Cyclodextrin Formed via Chiral Recognition with an AuI6AgI3CuII3 Molecular Cap

Solvent-mediated crystal-to-crystal transformations of [Au₆Ag₃Cu₃(H₂O)₃(d -pen)₆(tdme)₂]³⁺ (d -[ 1 (H₂O)₃]³⁺; pen²⁻= penicillaminate, tdme=1,1,1-tris(diphenylphosphinomethyl)ethane) to form unique supramolecular species are reported. Soaking crystals of d -[ 1 (H₂O)₃]³⁺ in aqueous Na₂bdc (bdc²⁻=1,4-benzenedicarboxylate) yielded crystals containing d -[ 1 (bdc)(H₂O)₂]⁺ due to the replacement of a terminal aqua ligand in d -[ 1 (H₂O)₃]³⁺ by a monodentate bdc²⁻ ligand. When γ-cyclodextrin (γ-CD) was added to aqueous Na₂bdc, d -[ 1 (H₂O)₃]³⁺ was transformed to d -[ 1 (bdc@γ-CD)(H₂O)₂]⁺, where a γ-CD ring was threaded by a bdc²⁻ molecule to construct a pseudorotaxane structure. While the use of dicarboxylates with an aliphatic carbon chain instead of bdc²⁻ afforded analogous pseudorotaxanes, such pseudorotaxane species were not formed when crystals of [Au₆Ag₃Cu₃(H₂O)₃(l -pen)₆(tdme)₂]³⁺ (l -[ 1 (H₂O)₃]³⁺) enantiomeric to d -[ 1 (H₂O)₃]³⁺ were soaked in aqueous Na₂bdc and γ-CD, affording only crystals containing l -[ 1 (bdc)(H₂O)₂]⁺.     

Revealing the composition-dependent structural evolution fundamentals of bimetallic nanoparticles through an inter-particle alloying reaction

Alloy nanoparticles represent one of the most important metal materials, finding increasing applications in diverse fields of catalysis, biomedicine, and nano-optics. However, the structural evolution of bimetallic nanoparticles in their full composition spectrum has been rarely explored at the molecular and atomic levels, imparting inherent difficulties to establish a reliable structure–property relationship in practical applications. Here, through an inter-particle reaction between [Au₄₄(SR)₂₆]²⁻ and [Ag₄₄(SR)₃₀]⁴⁻ nanoparticles or nanoclusters (NCs), which possess the same number of metal atoms, but different atomic packing structures, we reveal the composition-dependent structural evolution of alloy NCs in the alloying process at the molecular and atomic levels. In particular, an inter-cluster reaction can produce three sets of Au_xAg_44−x NCs in a wide composition range, and the structure of Au_xAg_44−x NCs evolves from Ag-rich [Au_xAg_44−x(SR)₃₀]⁴⁻ (x = 1–12), to evenly mixed [Au_xAg_44−x(SR)₂₇]³⁻ (x = 19–24), and finally to Au-rich [Au_xAg_44−x(SR)₂₆]²⁻ (x = 40–43) NCs, with the increase of the Au/Ag atomic ratio in the NC composition. In addition, leveraging on real-time electrospray ionization mass spectrometry (ESI-MS), we reveal the different inter-cluster reaction mechanisms for the alloying process in the sub-3-nm regime, including partial decomposition–reconstruction and metal exchange reactions. The molecular-level inter-cluster reaction demonstrated in this study provides a fine chemistry to customize the composition and structure of bimetallic NCs in their full alloy composition spectrum, which will greatly increase the acceptance of bimetallic NCs in both basic and applied research.

An inter-particle reaction between atomically precise [Au₄₄(SR)₂₆]²⁻ (SR = thiolate) and [Ag₄₄(SR)₃₀]⁴⁻ nanoparticles reveals the composition-dependent structural evolution of alloy Au_xAg_44−x nanoparticles at the atomic level.     

Positive Cooperativity Induced by Interstrand Interactions in Silver(I) Complexes with α,α′-Diimine Ligands

The allosteric positive cooperativity accompanying the formation of compact [Cu^I(α,α′-diimine)₂]⁺ building blocks contributed to the historically efficient synthesis of metal-containing catenates and knotted assemblies. However, its limited magnitude can easily be overcome by the negative chelate cooperativity that controls the overall formation of related polymetallic multistranded helicates and grids. Despite the more abundant use of analogous dioxygen-resistant [Ag^I(α,α′-diimine)₂]⁺ units in modern entangled metallo-supramolecular assemblies, a related thermodynamic justification was absent. Solid-state structural characterizations show the successive formation of [Ag^I(α,α′-diimine)(CH₃CN)][X] and [Ag^I(α,α′-diimine)₂][X] upon the stepwise reactions of α,α′-diimine=2,2′-bipyridine (bpy) or 1,10-phenanthroline (phen) derivatives with AgX (X=BF₄⁻, ClO₄⁻, PF₆⁻). In room-temperature, 5–10 mM acetonitrile solutions, these cationic complexes exist as mixtures in fast exchange on the NMR timescale. Spectrophotometric titrations using the unsubstituted bpy and phen ligands point to the statistical (=non-cooperative) binding of two successive bidentate ligands around Ag^I, a mechanism probably driven by the formation of hydrophobic belts, that overcomes the unfavorable decrease in the positive charge borne by the metallic cation. Surprisingly, the addition of methyl groups adjacent to the nitrogen donors (6,6′ positions in dmbpy; 2,9 positions in dmphen) induces positive cooperativity for the formation of [Ag(dmbpy)₂]⁺ and [Ag(dmphen)₂]⁺, a trend assigned to additional stabilizing interligand interactions. Adding rigid and polarizable phenyl side arms in [Ag(Brdmbpy)₂]⁺ further reinforces the positively cooperative process, while limiting the overall decrease in metal–ligand affinity.     

Na6(H2O)20(V10O28)·4H2O,a novel polyvanadate(V) with a three‐dimensional framework

The novel title polyvanadate(V), poly[[octa‐μ‐aqua‐dodecaaqua‐μ₄‐octacosaoxidodecavanadato‐hexasodium] tetrahydrate], [Na₆(H₂O)₂₀(V₁₀O₂₈)·4H₂O]_n, contains [V₁₀O₂₈]⁶⁻ anions which lie about inversion centres and have approximate 2/m symmetry and which are linked to [Na₃(H₂O)₁₀]³⁺ cations through two terminal and two μ₂‐bridging O atoms. The structure contains three inequivalent Na⁺ cations, two of which form [Na₂(H₂O)₈]_n chains, which are linked via NaO₆ octahedra involving the third Na⁺ ion, thus forming a three‐dimensional framework.     

THE METASTABLE PARTIALLY POSITIVELY CHARGED Se6 MOLECULE: PREPARATION,CHARACTERISATION AND X-RAY CRYSTAL STRUCTURE OF [Ag2(Se6)(SO2)2][Sb(OTeF5)6]2, [Ag2Se6][AsF6]2 AND [AgSe6][Ag2(SbF6)3]

Reactions designed to give Se₆[Sb(OTeF₅)₆]₂ by the reaction of Se₂Br₂, 4Se, and 2Ag[Sb(OTeF₅)₆] lead to products that include [Ag₂(Se₆)(SO₂)₂][Sb(OTeF₅)₆]₂(1). The distorted cubic (Ag₂Se₆ ²⁺) _n consists of a Se₆ molecule bicapped by two silver cations (local D_3d sym.). Reactions of AgMX₆ (M = As, Sb) with selenium in liquid SO₂ yielded crystals of [Ag₂Se₆][AsF₆]₂ (2) and [AgSe₆][Ag₂(SbF₆)₃] (3). Both salts contain stacked arrays of [AgSe₆]⁺ half-sandwich cationic units. [Ag₂Se₆][AsF₆]₂ in addition contains stronger, linear Se─Ag─Se horizontal linkages between the vertically stacked cationic columns. [AgSe₆][Ag₂(SbF₆)₃] features a remarkable three-dimensional [Ag₂(SbF₆)₃]^? anion held together by strong Sb─F···Ag contacts between component Ag⁺ and SbF₆ ^? ions. Hexagonal channels through this honeycomb-like anion are filled by the stacked [AgSe₆ ⁺]_x.     

LiZr4(PO4)3的Na/Li及Ag/Li离子交换

研究了LiZr2(PO4)3在水溶液中的Na/Li和Ag/Li离子交换行为.结果表明,LiZr2(PO4)3对Na+和Ag+离子均具有很高的选择性,且对Ag+的选择性高于Na+.LiZr2(PO4)3与Ag+的离子交换反应是通过形成固溶体的形式进行的,而与Na+的离子交换反应则是通过置换进行的.温度升高有利于提高LiZr2(PO4)3上Na/Li和Ag/Li的离子交换反应速度.     

Salts of Anionic Metal Carbonyl Clusters with Cryptand[2.2.2](Na+), DB‐18‐crown‐6(Na+), and Paramagnetic Cp*2Cr+ Cations Obtained by Reduction

Reduction of neutral metal clusters (Co₄(CO)₁₂, Ru₃(CO)₁₂, Fe₃(CO)₁₂, Ir₄(CO)₁₂, Rh₆(CO)₁₆, {CpMo(CO)₃}₂, {Mn(CO)₅}₂) by decamethylchromocene (Cp*₂Cr) or sodium fluorenone ketyl in the presence of cryptand[2.2.2] and DB‐18‐crown‐6 was studied. Nine new salts with paramagnetic Cp*₂Cr⁺, cryptand[2.2.2](Na⁺), and DB‐18‐crown‐6(Na⁺) cations and [Co₆(CO)₁₅]^2– ( 1 , 2 ), [Ru₆(CO)₁₈]^2– ( 3 – 4 ) dianions, [Rh₁₁(CO)₂₃]^3– ( 6 ) trianions, and new [Ir₈(CO)₁₈]^2– ( 5 ) dianions were obtained and structurally characterized. The increase of nuclearity of clusters under reduction was shown. Fe₃(CO)₁₂ preserves the Fe₃ core under reduction forming the [Fe₃(CO)₁₁]^2– dianions in 7 . The [CpMo(CO)₃]₂ and [Mn(CO)₅]₂ dimers dissociate under reduction forming mononuclear [CpMo(CO)₃]^– ( 8 ) and [Mn(CO)₅]^– ( 9 ) anions. In all anions the increase of negative charge on metal atoms shifts the bands attributed to carbonyl C–O stretching vibrations to smaller wavenumbers in agreement with the elongation of the C–O bonds in 1 – 9 . In contrast, the M–C(CO) bonds are noticeably shortened at the reduction. Magnetic susceptibility of the salts with Cp*₂Cr⁺ is defined by high spin Cp*₂Cr⁺ (S = 3/2) species, whereas all obtained anionic metal clusters and mononuclear anions are diamagnetic. Rather weak magnetic coupling between S = 3/2 spins is observed with Weiss temperature from –1 to –11 K. That is explained by rather long distances between Cp*₂Cr⁺ and the absence of effective π–π interaction between them except compound 7 showing the largest Weiss temperature of –11 K. The {DB‐18‐crown‐6(Na⁺)}₂[Co₆(CO)₁₅]^2– units in 2 are organized in infinite 1D chains through the coordination of carbonyl groups of the Co₆ clusters to the Na⁺ ions and π–π stacking between benzo groups of the DB‐18‐crown‐6(Na⁺) cations.     

Stability constants of complexes of Li+, H3O+, NH 4+ and Ag+ with hexaethyl calix[6]arene hexaacetate in nitrobenzene saturated with water

From extraction experiments and γ-activity measurements, the exchange extraction constants corresponding to the general equilibrium M⁺(aq)+NaL⁺(nb)⇔ML⁺(nb)+Na⁺(aq) taking place in the two-phase water-nitrobenzene system (M⁺ = Li⁺, H₃O⁺, NH₄⁺, Ag⁺; L = hexaethyl calix[6]arene hexaacetate; aq = aqueous phase, nb = nitrobenzene phase) were determined. Furthermore, the stability constants of the ML⁺ complexes in water saturated nitrobenzene were calculated; they were found to increase in the cation order H₃O⁺<NH₄⁺<Li⁺<Ag⁺.     

Towards clustered carbonyl cations [M3(CO)14]2+ (M = Ru,Os): the need for innocent deelectronation

To access the hitherto almost unknown class of clustered transition metal carbonyl cations, the trimetal dodecacarbonyls M₃(CO)₁₂ (M = Ru, Os) were reacted with the oxidant Ag⁺[WCA]⁻, but yielded the silver complexes [Ag{M₃(CO)₁₂}₂]⁺[WCA]⁻ (WCA = [Al(OR^F)₄]⁻, [F{Al(OR^F)₃}₂]⁻; R^F = –OC(CF₃)₃). Addition of further diiodine I₂ to increase the redox potential led for M = Ru non-specifically to divalent mixed iodo-Ru^II-carbonyl cations. With [NO]⁺, even the N–O bond was cleaved and led to the butterfly carbonyl complex cation [Ru₄N(CO)₁₃]⁺ in low yield. Obviously, ionization of M₃(CO)₁₂ with retention of its pseudo-binary composition including only M and CO is difficult and the inorganic reagents did react non-innocently. Yet, the radical cation of the commercially available perhalogenated anthracene derivative 9,10-dichlorooctafluoroanthracene (anthracene^Hal) is a straightforward accessible innocent deelectronator with a half-wave potential E_1/2 of 1.42 V vs. Fc^0/+. It deelectronates M₃(CO)₁₂ under a CO atmosphere and leads to the structurally characterized cluster salts [M₃(CO)₁₄]²⁺([WCA]⁻)₂ including a linear M₃ chain. The structural characterization as well as vibrational and NMR spectroscopies indicate the presence of three electronically independent sets of carbonyl ligands, which almost mimic M(CO)₅, free CO and even [M(CO)₆]²⁺ in one and the same cation.

Trimeric M₃(CO)₁₂ (M = Ru, Os) reacts with typical inorganic oxidants to unwanted side products. Yet, the 9,10-dichlorooctafluoroanthracene radical cation deelectronates these under CO pressure to give the first homotrimetallic [M₃(CO)₁₄]²⁺ salts.     

The Crystal Structure of Solvent‐Free Silver Dodecachloro‐closo‐dodecaborate Ag2[B12Cl12] from Aqueous Solution

Colourless octahedral single crystals of solvent‐free Ag₂[B₁₂Cl₁₂] (cubic, Pa3¯; a = 1238.32(7) pm, Z = 4) are obtained by the metathesis reaction of Cs₂[B₁₂Cl₁₂] with an aqueous solution of silver nitrate (AgNO₃) and recrystallization of the crude product from water. The crystal structure is best described as a distorted anti‐CaF₂‐type arrangement in which the quasi‐icosahedral [B₁₂Cl₁₂]^2— anions (d(B—B) = d(B—Cl) = 177—180 pm) are arranged in a cubic closest‐packed fashion. The tetrahedral interstices are filled with Ag⁺ cations which are strongly displaced from their ideal positions. Thereby each silver atom gets coordinated by six chlorine atoms from the edges of three [B₁₂Cl₁₂]^2— anions providing a distorted octahedral coordination sphere to the Ag⁺ cations (d(Ag—Cl) = 283—285 pm, CN = 6).     

Crystal Structure and Thermal Stability of Ag3(CHF2COO)3(H2O)2

X-ray diffraction analysis of [Ag₃(CHF₂COO)₃(H₂O)₂] revealed that its crystals are orthorhombic: space group Cmca, a = 13.809(4) Å, b = 15.975(2) Å, c = 12.244(2) Å, Z = 8. The thermogravimetric analysis showed that under the atmosphere of N₂ and at 101.3 kPa, silver difluoroacetate melts at 488 K; the thermal decomposition reaction occurs in the interval 493–548 K with the formation of Ag. Under the mass-spectral experiment conditions at 521 K, two processes occur simultaneously, namely, evaporation and decomposition. The following ions were detected in the mass-spectrum of silver difluoroacetate: Ag₂L⁺, Ag₂R⁺, Ag₂F⁺, Ag₂O⁺, Ag₂ ⁺, Ag⁺, LH⁺, RCO⁺, R⁺ (L = CHF₂COO, R = CHF₂).     

Na1.89Ag0.11[BP2O7(OH)] und Na2[BP2O7(OH)] – Isotype Borophosphate mit Tetraeder-Schichtpaketen

Na_1.89Ag_0.11[BP₂O₇(OH)] and Na₂[BP₂O₇(OH)] – Isotypic Borophosphates Containing Layered Tetrahedral Blocks The isotypic borophosphates Na_1.89Ag_0.11[BP₂O₇(OH)] and Na₂[BP₂O₇(OH)] were grown under mild hydrothermal conditions (T = 165–170 °C). The crystal structures were solved by single crystal methods in the case of Na_1.89Ag_0.11[BP₂O₇(OH)] and by refinement of powder data (Rietveld method) for Na₂[BP₂O₇(OH)], respectively (orthorhombic, Pna2₁ (No. 33); a = 683.98(14)/682.36(1) pm, b = 2086.5(4)/2079.11(4) pm, c = 1318.9(3)/1314.46(3) pm; Z = 12). The compounds contain a complex two-dimensional structure consisting of layered tetrahedral blocks, which are formed by six- and eight-membered rings of tetrahedra. The Na⁺/Ag⁺-ions are located inside and near the surface of the ‘layer blocks' and are five-, six- and sevenfold coordinated by oxygen.     

Novel heptavalent actinide compounds: tetrasodium dihydroxidotetraoxidoneptunate(VII) hydroxide dihydrate and its plutonium analogue

The title compounds, Na₄[NpO₄(OH)₂]OH·2H₂O and Na₄[PuO₄(OH)₂]OH·2H₂O, are isostructural and isomorphous, and contain complex [AnO₄(OH)₂]³⁻ anions (Ac is an actinide) in the form of distorted tetragonal bipyramids, Na⁺ cations, crystallization water molecules and outer‐sphere OH groups. The complex [AnO₄(OH)₂]³⁻ anions occupy general positions and the coordinated OH groups deviate significantly from a centrosymmetric relative orientation. The [AnO₄(OH)₂]³⁻ anions exhibit anisotropic actinide contraction; the shortening of the An—O(hydroxide) bonds on going from Np to Pu is greater than that of the AnO₄ groups.