Alkaline Earth Guests in Polyoxopalladate Chemistry: From Nanocube to Nanostar via an Open‐Shell Structure

The three novel, discrete palladium(II)‐oxo clusters [CaPd₁₂O₈(PhAsO₃)₈]^6? ( CaPd₁₂ ), [SrPd₁₂O₆(OH)₃(PhAsO₃)₆(OAc)₃]^4? ( SrPd₁₂ ), and [BaPd₁₅O₁₀(PhAsO₃)₁₀]^8? ( BaPd₁₅ ) encapsulating alkaline earth metal ions were prepared and fully characterized by a multitude of solution and solid‐state physicochemical techniques. We have discovered a structure‐directing template effect induced by the respective size of the alkaline earth guest ion, which determines the detailed condensation arrangement of the peripheral Pd^II‐oxo shell. The unprecedented SrPd₁₂ with an open‐shell type structure is of particular importance and reflects a successful strategy for deliberate design of new structural classes of polyoxo‐noble‐metalates. Furthermore, the unusual acetate–water ligand exchange phenomenon renders SrPd₁₂ as a promising candidate for noble‐metal‐based catalysis.     

Diffractive and non-diffractive pion production on deuterons

We present an ensemble of formulae for the calculation of the Glauber correction to incoherent production on deuterons. The formulae are written in terms of phases, slopes and integrated cross sections and both the diffractive and non-diffractive case are considered. It is shown in the case K⁺ → K⁰π⁺, that only if the analysis is done in such a way that the final set of states is complete, is there agreement between theory and experiment.     

Synthesis and structure of dilacunary decatungstogermanate, [gamma-GeW10O36]8-

The dilacunary decatungstogermanate [gamma-GeW10O36]8- (1) has been synthesized and structurally characterized in solution and in the solid state. Reaction of germanium dioxide with sodium tungstate in aqueous acidic medium results in the formation of [beta2-GeW11O39]8- (2), which is then used as a precursor for the synthesis of 1. The (183)W spectrum of 2 shows the expected 11 peaks of equal intensity, whereas that of 1 exhibits the expected three peaks with relative intensities 2:2:1. Polyanion 1 represents a novel lacunary polyoxometalate, giving rise to a multitude of derivatives by reaction with transition metals, lanthanides, and other electrophiles.     

Spectroscopic investigations of ADMA encapsulated in pyrogallol[4]arene nanocapsules

Pyrogallol[4]arenes form stable hydrogen-bonded nanocapsules that have unique properties that may make them suitable for diverse applications, such as catalysts and molecular transporters. Little is known about the behavior of the interior of these new materials in solution, and by using the solvent-dependent properties of 1-(9-anthryl)-3-(4-dimethylaniline) propane (ADMA), the inner phase properties of the hexamers are investigated. Steady-state and dynamic spectrofluorometric results are in agreement, are consistent with solid-state studies, and indicate that the majority of ADMA is sequestered in an extended conformation with the crystallization solvent. The conformational flexibility of ADMA is attributed to lower capsule occupancies ( approximately 50%, i.e., 1 molecule per 2 capsules, one occupied and one empty) relative to our previous study with pyrene butyric acid (occupancy of 150%, i.e., 1.5 molecules per capsule) in which the probe was restricted within a nanocapsule. The nature of the encapsulated ADMA complexes are found to change with time, as there is either fluorophore leaching from the capsule or endo-exo-capsule solvent exchange. However, the choice of crystallizing solvent (ethyl acetate or acetonitrile) and PgC(n) alkyl tail (C(6) or C(10)) does not influence experimental outcomes. These research findings give a better understanding of the encapsulation versatility of these unique supramolecular assemblies and the protective nanopockets that can exist for guest molecules.     

6-Peroxo-6-zirconium crown and its hafnium analogue embedded in a triangular polyanion: [M6(O2)6(OH)6(gamma-SiW10O36)3]18- (M = Zr, Hf)

We have synthesized and structurally characterized the unprecedented peroxo-zirconium(IV) containing [Zr6(O2)6(OH)6(gamma-SiW10O36)3]18- (1). Polyanion 1 comprises a cyclic 6-peroxo-6-zirconium core stabilized by three decatungstosilicate units. We have also prepared the isostructural hafnium(IV) analogue [Hf6(O2)6(OH)6(gamma-SiW10O36)3]18- (2). We investigated the acid/base and redox properties of 1 by UV-vis spectroscopy and electrochemistry studies. Polyanion 1 represents the first structurally characterized Zr-peroxo POM with side-on, bridging peroxo units. The simple, one-pot synthesis of 1 and 2 involving dropwise addition of aqueous hydrogen peroxide could represent a general procedure for incorporating peroxo groups into a large variety of transition metal and lanthanide containing POMs.     

Cation Effect on Formation of Preyssler‐type 30‐Tungsto‐5‐phosphate: Enhanced Yield of Na‐encapsulated Derivative and Direct Synthesis of Ca‐ and Bi‐Encapsulated Derivatives

The effect of cations in a reaction mixture for the preparation of the Preyssler‐Jeannin‐Pope type 30‐tungsto‐5‐phosphate [P₅W₃₀O₁₁₀Na]^14– is investigated. Reaction of phosphate and tungstate with a P/W ratio of ca. 3.9 in an acidic aqueous solution without cations selectively leads to the Dawson‐type 18‐tungsto‐2‐phosphate, [P₂W₁₈O₆₂]^6–. Amongst all the alkali cations, only Na⁺ allows formation of the Preyssler‐type polyanion [P₅W₃₀O₁₁₀Na]^14–, with an encapsulated Na⁺ ion, and the product yield can be improved by increasing Na⁺ amount. The presence of Li⁺ ions instead results in the Dawson‐type polyanion [P₂W₁₈O₆₂]^6–, whereas K⁺, Rb⁺, and Cs⁺ selectively result in the Keggin‐type polyanion [PW₁₂O₄₀]^3–. An improved synthetic procedure for the Na⁺‐encapsulated Preyssler‐ion leading to a higher isolated yield is presented. Furthermore, addition of Ca²⁺ and Bi³⁺ compounds allows formation of the Ca²⁺‐ and Bi³⁺‐encapsulated Preyssler‐type polyanions, [P₅W₃₀O₁₁₀Ca]^13– and [P₅W₃₀O₁₁₀Bi]^12–, respectively. Furthermore, single‐crystal XRD structure of the Bi³⁺‐encapsulated Preyssler‐type polyanions, [P₅W₃₀O₁₁₀Bi]^12–, is presented for the first time.     

NiII36-Containing 54-Tungsto-6-Silicate: Synthesis,Structure, Magnetic and Electrochemical Studies

The 36-Ni^II-containing 54-tungsto-6-silicate, [Ni₃₆(OH)₁₈(H₂O)₃₆(SiW₉O₃₄)₆]⁶⁻ ( Ni₃₆ ) was synthesized by a simple one-pot reaction of the Ni₂-pivalate complex [Ni₂(μ-OH₂)(O₂CCMe₃)₄(HO₂CCMe₃)₄] with the trilacunary [SiW₉O₃₄]¹⁰⁻ polyanion precursor in water and structurally characterized by a multitude of physicochemical techniques including single-crystal XRD, FTIR, TGA, elemental analysis, magnetic and electrochemical studies. Polyanion Ni₃₆ comprises six equivalent {Ni^II₆SiW₉} units which are linked by Ni−O−W bridges forming a macrocyclic assembly. Magnetic studies demonstrate that the {Ni₆} building blocks in Ni₃₆ remain magnetically intact while forming a hexagonal ring with antiferromagnetic exchange interactions between adjacent {Ni₆} units. Electrochemical studies indicate that the first reduction is reversible and associated with the W^VI/V couple, whereas the second reduction is irreversible attributed to the Ni^II/0 couple.     

Kinetic study of the nitric oxide oxidation between 288 and 323 K,under pressure,focus on the oxygen influence on the reaction rate constant

The sequestration of carbon dioxide fumes from oxyfuel combustion is used to reduce significantly the carbon dioxide emissions from coal-fired power plants. Impurities like nitric oxide, present in the fumes, can cause technical difficulties during the capture, the treatment, the transport, and the storage steps of the CO₂ fumes. The purpose of this study is to better understand the oxidation of nitric oxide under pressure in the presence of carbon dioxide and in the experimental condition of flue gas treatment. This reaction is known to be a third-order reaction, two order in nitric oxide and first order in oxygen. To examine the effect of the temperature, the pressure and the volume fraction of oxygen on the rate constant of oxidation, k₁, an autoclave is used. The first experiment studies the influence of the temperature between 288 and 323 K. The results found are in the form of an Arrhenius-type equation: k₁ = 810 exp^(620/T) and are in agreement with the literature. Carbon dioxide does not seem to have an influence on the rate constant, whereas our experimental measurements indicate an influence of the volume fraction of oxygen. The rate constant decreases when the oxygen volume fraction increases by up to 10%. Then the rate constant remains constant. This observation allows us to conclude that the mechanism involving the mechanism with a dimer of NO as an intermediate is more likely to be the mechanism involved in the nitric oxide oxidation in our experimental conditions: high pressure and ambient temperature. The rate constant k₂, k_–2, and k₃ were also estimated in these conditions.     

Organoantimony(III)‐Containing Tungstoarsenates(III): From Controlled Assembly to Biological Activity

A family of three sandwich‐type, phenylantimony(III)‐containing tungstoarsenates(III), [(PhSb^III){Na(H₂O)}As^III₂W₁₉O₆₇(H₂O)]^11? ( 1 ), [(PhSb^III)₂As^III₂W₁₉O₆₇(H₂O)]^10? ( 2 ), and [(PhSb^III)₃(B‐α‐As^IIIW₉O₃₃)₂]^12? ( 3 ), have been synthesized by one‐pot procedures and isolated as hydrated alkali metal salts, Cs₃K_3.5Na_4.5[(PhSb^III){Na(H₂O)}As^III₂W₁₉O₆₇(H₂O)]?41H₂O ( CsKNa ‐ 1 ), Cs_4.5K_5.5[(PhSb^III)₂As^III₂W₁₉O₆₇(H₂O)]?35H₂O ( CsK‐2 ), and Cs_4.5Na_7.5[(PhSb^III)₃(B‐α‐As^IIIW₉O₃₃)₂]?42H₂O ( CsNa ‐ 3 ). The number of incorporated {PhSb^III} units could be selectively tuned from one to three by careful control of the reaction parameters. The three compounds were characterized in the solid state by single‐crystal XRD, IR spectroscopy, and thermogravimetric analysis. The aqueous solution stability of sandwich polyanions 1 – 3 was also studied by multinuclear (¹H, ¹³C, ¹⁸³W) NMR spectroscopy. Effective inhibitory activity against six different kinds of bacteria was identified for all three polyanions, for which the activity increased with the number of incorporated {PhSb^III} groups.