Solvatation des ions par le nitromethane

The direct potentiometric determination of the normal potentials of Cu/Cu⁺, Cu⁺/Cu²⁺, Ag/Ag⁺, Hg/Hg²⁺₂ couples in nitromethane and the comparison of these values with the normal potentials in aqueous solution makes possible the calculation of solvation coefficients γ_(t)(Mⁿ⁺) of the corresponding cations; the Strehlow hypothesis (γ(Fc) = γ(Fc⁺)) has been used. An indirect method using the determination of the solubility constants of alkaline chlorides and alkaline earth chlorides leads to the normal potentials of alkaline and Mg²⁺ cations and thus to the γ_(t) values of these ions.The measures of the AgX^-₂ stability constants and of the AgX solubility constants lead to the γ_(t) values of X^? and AgX^?₂ anions (X^? = Cl^?, Br^?, I^?, Scn^?, CH₃CO^?₂, CN^?, BrO^?₃, (C₆H₅)₄B^?). A comparison of γ_(t)(H⁺) and γ_(t)(Ag⁺) for 20 solvents is given.     

Cation field-strength effects on ion irradiation-induced mechanical property changes of borosilicate glass structures

We examine the impact of the glass network-modifier cation field strength (CFS) on ion irradiation-induced mechanical property changes in borosilicate (BS) glasses for the ternary M₂O–B₂O₃–SiO₂ systems with M = {Na, K, Rb} and the quaternary [0.5M₍₂₎O–0.5Na₂O]–B₂O₃–SiO₂ systems with M = {Li, Na, K, Rb Mg, Ca, Sr, Ba}. ¹¹B nuclear magnetic resonance (NMR) experiments on the as-prepared BS glasses yielded the fractional population of four-coordinated B species (B^[4]) out of all {B^[3], B^[4]} groups in the glass network, along with the fraction of B^[4]–O–Si linkages out of all B^[4]–O–Si/B bonds. Both parameters correlated linearly with the (average) CFS of the M⁺ and/or {M⁽²⁾⁺, Na⁺} cations. Both the nanoindentation-derived hardness and Young's modulus values of the glasses reduced upon their irradiation by Si²⁺ ions, with the property deterioration decreasing linearly with increasing M^z+ CFS, that is, for higher M^z+⋅⋅⋅O interaction strength. The irradiation damage of the glass network also increased linearly with the fraction of B^[4]–O–Si linkages, which are the second weakest in the structure after the M^z+⋅⋅⋅O bonds. Our results underscore the advantages of employing BS glasses with high-CFS cations for enhancing the radiation resistance for nuclear waste storage.     

A bipolar electrospray source of singly charged salt clusters of precisely controlled composition

The few clusters [B^?_nA⁺_n+1]⁺ (n = 0,1) with resolvable mobilities formed in electrosprays of large salts have been used for nanoparticle instrument testing and calibration at sizes smaller than 2 nm. Extensions of this modest size range by charge reduction with uncontrolled gas phase ions has resulted in impure singly charged clusters. Here, we combine two oppositely charged electrosprays of solutions of the same salt B^?A⁺, including: (C_nH_2n+1)₄N⁺Br^? (n = 4,7,12,16), the large phosphonium cation (C₆H₁₃)₃(C₁₆H₃₃)P⁺ paired with the anions Im^? [(CF₃SO₂)₂N^?] or FAP^? [(C₂F₅)₃PF₃^?], and the asymmetric pair [1-methyl-3-pentylimidazolium⁺FAP^?]. Both polarities are simultaneously produced by this source in comparable abundances, primarily as singly charged A⁺_nB^?_n±1, with tiny contributions from higher charge states. Some but not all of these clusters produce narrow mobility peaks typical of pure ions, even beyond n = 43. Excellent independent stable control of the positive and the negative sprays brought very close to each other is achieved by isolating them electrostatically with a symmetrically interposed metallic screen. Two nanoDMAs covering the size range up to 30 nm (Halfmini and Herrmann DMAs, with classification lengths of 2 and 10 cm) are characterized with these standards, revealing resolving powers considerably higher than previously seen with unipolar electrospray sources. The bipolar source of pure and chemically homogeneous clusters described permits studying size and charge effects in a variety of aerosol instruments in the 1–4 nm size range.

Copyright © 2017 American Association for Aerosol Research     

Neutral Dissociation of Pyridine Evoked by Irradiation of Ionized Atomic and Molecular Hydrogen Beams

The interactions of ions with molecules and the determination of their dissociation patterns are challenging endeavors of fundamental importance for theoretical and experimental science. In particular, the investigations on bond-breaking and new bond-forming processes triggered by the ionic impact may shed light on the stellar wind interaction with interstellar media, ionic beam irradiations of the living cells, ion-track nanotechnology, radiation hardness analysis of materials, and focused ion beam etching, deposition, and lithography. Due to its vital role in the natural environment, the pyridine molecule has become the subject of both basic and applied research in recent years. Therefore, dissociation of the gas phase pyridine (C₅H₅N) into neutral excited atomic and molecular fragments following protons (H⁺) and dihydrogen cations (H₂⁺) impact has been investigated experimentally in the 5–1000 eV energy range. The collision-induced emission spectroscopy has been exploited to detect luminescence in the wavelength range from 190 to 520 nm at the different kinetic energies of both cations. High-resolution optical fragmentation spectra reveal emission bands due to the CH(A²Δ→X²Π_r; B²Σ⁺→X²Π_r; C²Σ⁺→X²Π_r) and CN(B²Σ⁺→X²Σ⁺) transitions as well as atomic H and C lines. Their spectral line shapes and qualitative band intensities are examined in detail. The analysis shows that the H₂⁺ irradiation enhances pyridine ring fragmentation and creates various fragments more pronounced than H⁺ cations. The plausible collisional processes and fragmentation pathways leading to the identified products are discussed and compared with the latest results obtained in cation-induced fragmentation of pyridine.     

Stereocomplex formation between enantiomeric poly(lactic acid)s. X. Binary blends from poly(D-lactide-CO-glycolide) and poly(L-lactide-CO-glycolide)

Binary blend films from lactide-rich poly(D -lactide-co-glycolide) (PDLG) and poly(L -lactide-co-glycolide) (PLLG) were obtained by casting methylene chloride solutions of the two mixed copolymers with different D- and L-lactide contents (X_DI and X_LI ), and their crystallization was studied by differential scanning calorimetry (DSC). Four combinations were selected from the binary (A-B) blends: mixing of the same polymer [X_DI (A) = X_DI (B) or X_LI (A) = X_LI(B)], blending under X_DI (B) = X_LI (A), blending of a D -lactide homopolymer [X_DI(B) = 1] with other PDLGs, and blending of a D -lactide homopolymer [X_DI(B) = 1] with other PLLGs. Racemic crystallites were exclusively formed between PDLG and PLLG when they had high lactide unit contents. The melting point and enthalpy of fusion of the racemic crystallites decreased with a decrease in X_DI of PDLG or X_LI of PLLG, suggesting that glycolide units in the polymer disturbed the growth of the racemic crystallites. A similar behavior was also observed for the homocrystallization in nonblended copolymer films. Homocrystallites composed entirely either of D -lactide unit or L-lactide unit sequences were formed when one component was crystallizable and the other component had the same sign of optical rotation or very different lactide content. An interesting finding was that even nonhomocrystallizable lactide-poor PDLG and PLLG could form racemic crystallites when both were blended. © 1994 John Wiley & Sons, Inc.     

Crystal structure of Kuzel's salt 3CaO·Al2O3·1/2CaSO4·1/2CaCl2·11H2O determined by synchrotron powder diffraction

The crystal structure of Kuzel's salt has been successfully determined by synchrotron powder diffraction. It crystallizes in the rhombohedral R3? symmetry with a = 5.7508 (2) Å, c = 50.418 (3) Å, V = 1444.04 (11) ų. Joint Rietveld refinement was realized using three X-ray powder patterns recorded with a unique wavelength and three different sample-to-detector distances. Kuzel's salt is the chloro-sulfoaluminate AFm phase and belongs to the layered double hydroxide (LDH) large family. Its structure is composed of positively charged main layer [Ca₂Al(OH)₆]⁺ and negatively charged interlayer [Cl_0.50·(SO₄)_0.25·2.5H₂O]⁻. Chloride and sulfate anions are ordered into two independent crystallographic sites and fill successive interlayer leading to the formation of a second-stage compound. The two kinds of interlayer have the compositions [Cl·2H₂O]⁻ and [(SO₄)_0.5·3H₂O]⁻. The crystal structure explains why chloride and sulfate anions are not substituted and why the formation of extended solid solution in the chloro-sulfate AFm system does not occur.     

Collisional Probing of the Transition-State Structure of a Bimolecular Reaction

The total cross section σ_B(E) for the Ca(¹D) + HBr → CaBr(B²Σ⁺) + H reaction as a function of collision energy has been measured using crossed atomic and molecular beams. The maxima exhibited by σ_B(E) with increasing energy are attributed to the opening of successive bending vibrational reaction channels that proceed via a [Ca(¹D) ⃛ Br ⃛ H]^‡ transition state. A dynamical model for the reaction may be constructed in terms of Landau-Zener probabilities for curve crossing at two locations on the reaction path, coupled with a preference for consumption of transition-state vibrational energy.     

Ab Initio Molecular Orbital Study of Electronic and Geometrical Structures of MCH2+ Complex and its Reactivity with H2, Where M = Co,Rh, and Ir

By using CASSCF (for optimization of geometries) and MR-SDGI-CASSCF (for energies) methods we have studied and compared the mechanism of reaction MCH₂⁺ + H₂, as well as the electronic and geometrical structure of the MCH₂⁺ complex, where M = Co, Rh, and Ir. It has been found that the mechanisms of reaction MCH₂⁺ + H₂ → M⁺ + CH₄ (1) for M = Co and Rh are similar and follow the path: MCH₂⁺+H₂ → (H₂)MCH₂⁺ → [TS1, H₂-activation] → MCH₄⁺ → M⁺ + CH₄. The key step is activation of the H-H bond, which has a barrier about twice as high for M = Co as for M = Rh; reaction ( 1 ) occurs more easily for M = Rh than M = Co. M = Ir completely changes the mechanism of reaction ( 1 ), which now follows the path: IrCH₂⁺(³A₂) + H₂ → (H₂) IrCH₂⁺(³A₂) → [TS1, H₂-activation] → (H)₂ IrCH₂⁺(¹A') → [TS2, H-migration] → HIrCH₃⁺(³A) → [TS3, CH₄-elimination] → IrCH₄⁺(³A₂) → Ir⁺(⁵F, s¹d⁷) + CH₄. The reaction ( 1 ) is exothermic for M = Co and Rh, but endothermic for M = Ir. For M = Co and Rh, the reverse reaction M⁺ + CH₄ can give only one product MCH₄⁺ and does not proceed further easily; for M = Co, at elevated temperature CoCH₄⁺may give CoH⁺ and CoCH₃⁺. However, for M = Ir the reverse reaction can proceed further to give hydridomethyl HIrCH₃⁺ and bishydrido (H)₂CH₂⁺ complexes, as well as IrCH₄⁺.     

Structure of the epoxy–chelate metal-containing matrices: Theoretical aspects

A theoretical analysis has been carried out of the structure of metalliferous epoxy–chelate polymers (MECP) based on diglycidyl ether of bisphenol-A (DGEBA) hardened with metal complexes of the formula [M(L)_n(X)_p], where M is the cation of the transition metal; R, a nitrogen-containing ligand; X, the anion of an organic acid; n, the number of the ligands in the complex molecule (n = 1 or 2), and p, the metal valency (p = 2 or 3). On the basis of the correlations between the tensile strength (σ_t) and tensile modulus (E_t), and flexural strength (σ_f) and flexural modulus (E_f), of MECP, σ_t = f(E_t)and σ_f = f(E_f), and supposing that when the condition $ \sigma _{_{t_A } }= \sigma _{_{t_B } } ,{\rm}\sigma _{_{f_A } }= \sigma _{f_B } ,{\rm}E_{t_A }= E_{t_B } ,{\rm}E_{f_A }= E_{f_B } $ is fulfilled, where A and B are complex hardeners of different structures but of the same class, the epoxy–chelate matrices have similar structures. The influence of the structural fragments of the hardener molecule (the metal, ligand, and anion) on the polymer properties was evaluated and it was found out that the biggest contribution to these properties belongs to the metal, the alteration of which changes the thermal stability (ΔM is the polymer mass loss after thermal treatment in air), deformability (ε), σ_f, E_f, and deflection temperature (DT) significantly. By this, the effect of the hardener structure change on the alteration of the MECP properties is maximal for ΔM, is minimal for the compressive strength (σ_c), and decreases in the series: ΔM > ε > DT > σ_f > E_f > σ_c. The type of the anion affects σ_c significantly, but the ligand type contributes the least to the polymer properties. The obtained dependencies of the MECP properties on the structural fragments of the complex hardeners allow preliminary evaluation of the structure of the chelates and epoxy–chelate compositions necessary to produce epoxy polymers with required properties. The new method of the theoretical investigation of the effect of the structural fragments (method of TIESF) of the polymer matrix on the polymer properties can be used to analyze the structures of the polymers of other classes and to predict the optimal structures, promising the production of the materials with the optimal properties. © 1993 John Wiley & Sons, Inc.     

Blends of aliphatic polyesters. I. Physical properties and morphologies of solution-cast blends from poly(DL-lactide) and poly(ε-caprolactone)

Effects of the mixing ratio of poly(DL-lactide) (PDLLA) and poly (ε-caprolactone) (PCL) on the thermal and mechanical properties and morphologies of the solution-cast blends were investigated by differential scanning calorimetry (DSC), polarizing microscopy, tensile tests, and dynamic mechanical analysis. The presence of amorphous PDLLA did not disturb crystallization of PCL over the PDLLA content [X_PDLLA = PDLLA/(PCL + PDLLA)] from 0.1 to 0.9 and allowed PCL to form spherulites over X_PDLLA ranging from 0.1 to 0.6. The spherulite radius was larger for the blends than for the nonblended PCL. Phase separation occurred for the blends with X_PDLLA between 0.1 and 0.9 T^m of PCL remained unchanged in the X_PDLLA range up to 0.6 but decreased at X_PDLLA above 0.6, whereas the crystallinity of PCL was constant around 60%, irrespective of X_PDLLA. The tensile strength (σ_B, the yield stress (σ_Y), the Young's modulus(E), and the storage modulus (G′) of the blends increased monotonously with X_PDLLA if σ_B at X_PDLLA = 0 and 0.6 and σ_Y at X_PDLLA = 0.6 were excluded. Elongation-at-break (ε_B) of PDLLA increased dramatically, while ε_B of PCL decreased remarkably when a small amount of the other component was added. Equations and parameters predicting σ_Y, E, and G′ of the PCL-PDLLA blends were proposed as a function of X_PDLLA. © 1996 John Wiley & Sons, Inc.     

Wechselwirkungen in Kristallen. 98. Mitt. Protonierte Hexamethylmelamin-Salze mit verschiedenen Anionen: Monomeres Tetraphenylborat,dimeres Trifluoracetat und polymeres Chlorid-Dihydrat

Interaction in Crystals. 98. Protonated Hexamethylmelamin Salts with Different Anions: Monomeric Tetraphenylborate, Dimeric Trifluoracetate and Polymeric Chloride-Dihydrate Hexamethylmelamin (2,4,6-tris(dimethylamino)-1,3,5-triazine), on monoprotonation at one of the triazine nitrogens keeps its close to planar skeleton. Its salts with different anions reflect biochemically interesting hydrogen-bridge networks: Crystallization of the hydrochloride from isopropanol solution containing Li^⊕ [B^⊖(C₆H₅)₄], yields “naked” molecular cations, packed in herringbone fashion in between the lattice-dominating bulky, phenyl-shielded and non-protonable tetraphenylborate anions. From trifluoroacetic acid, crystals with sandwich-like subunits connected by hydrogen-bridged anions [F₃CCOO^⊖…︁HOOCCF₃] are obtained. The hydrochloride salt, prepared by adding aqueous HCl to a diethylether solution, crystallizes in stacks of triazinium cation dimers with an intermolecular bridge N^⊕-H…︁Cl^⊖…︁H^⊕N in between chloride-bydrate strands (…︁Cl^⊖…︁HOH…︁O(H)H…︁Cl^⊖…︁). Together, the structures of the three different hexamethyl-melaminium salts further illustrate the influence of anions on the crystallization of protonated nitrogen heterocycles and complement that of counter cation cation solvation in molecular anion salts.     

Expanding the chemistry of single‐ion conducting poly(ionic liquid)s with polyhedral boron anions

The synthesis of a new family of single‐ion conducting random copolymers bearing polyhedral boron anions is reported. For this purpose two novel ionic monomers, namely [B₁₂H₁₁(OCH₂CH₂)₂OC(?O)C(CH₃)?CH₂]^2?[(C₄H₉)₄N⁺]₂ and [8‐(OCH₂CH₂)₂OC(?O)C(CH₃)?CH₂‐3,3′‐Co(1,2‐C₂B₉H₁₀)(1′,2′‐C₂B₉H₁₁)]^?K⁺, having methacrylate function, diethylene glycol bridge and closo‐dodecaborate or cobalt bis(1,2‐dicarbollide) anions were designed. Such monomers differ from previously reported ones by (i) chemically attached highly delocalized boron anions, by (ii) valency of the anion (divalent anion and monovalent one) and by (iii) the presence of oxyethylene flexible spacer between the methacrylate group and bonded anion. Their free radical copolymerization with poly(ethylene glycol) methyl ether methacrylate and subsequent ion exchange provided lithium‐ion conducting polyelectrolytes showing low glass transition temperature (?53 to ?49 °C), ionic conductivity up to 9.1 × 10^?7 S cm^?1, lithium transference number up to 0.61 (70 °C) and electrochemical stability up to 4.1 V versus Li⁺/Li (70 °C). The incorporation of propylene carbonate (20–40 wt%) into the copolymers resulted in the enhancement of their ionic conductivity by one order of magnitude and significantly increased their electrochemical stability up to 4.7 V versus Li⁺/Li (70 °C). © 2019 Society of Chemical Industry     

Impact of the cation field strength on physical properties and structures of alkali and alkaline-earth borosilicate glasses

The impact of the cation field strength (CFS) of the glass network-modifier cations on the structure and properties of borosilicate glasses (BS) were examined for a large ensemble of mixed-cation (R/2)M₍₂₎O–(R/2)Na₂O–B₂O₃–KSiO₂ glasses with M⁺ ={Li⁺, Na⁺, K⁺, Rb⁺} and M²⁺ ={Mg²⁺, Ca²⁺, Sr²⁺, Ba²⁺} from four series of {K, R} combinations of K = n(SiO₂)/n(B₂O₃) = {2.0, 4.0} and R =[n(M₍₂₎O) ?+ ?n(Na₂O)]/n(B₂O₃) = {0.75, 2.1}. Combined with results from La³⁺ bearing glasses enabled the probing of physical-property variations across a wide CFS range, encompassing the glass transition temperature (T_g), density, molar volume and compactness, as well as the hardness (H) and Young's modulus (E). We discuss the inferred composition–structure/CFS–property relationships. Each of T_g, H, and E revealed a non-linear dependence against the CFS and a strong T_g/H correlation, where each property is maximized for the largest alkaline-earth metal cations, i.e., Sr²⁺ and Ba²⁺, along with the high-CFS La³⁺ species. The ¹¹B MAS NMR-derived fractional BO₄ populations decreased linearly with the average M^z+/Na⁺ CFS within both K–0.75 glass branches, whereas the NBO-rich K–2.1 glasses manifested more complex trends. Comparisons with results from RM₂O–B₂O₃–KSiO₂ glasses suggested no significant “mixed alkali effect”.     

Wechselwirkungen in Kristallen. 96. Darstellung und Strukturen von Salzen [RnN⊕H…︁NRn][B⊖(C6H5)4] mit Prototyp-Wasserstoffbrücken N⊕H…︁N

Interactions in Crystals. 96. Preparation and Structures of Salts [R_nN^⊕H…︁NR_n][B^⊖(C₆H₅)₄] with Prototype Hydrogen Bridges N^⊕H…︁N Straightforward crystallization of ammonium salts [R_nN^⊕H] X^⊖ added lithium tetraphenylborate, and amine R_nN from acetone solution yields salts [R_nN^⊕H…︁NR_n][B^⊖(C₆H₅)₄] with the (under the conditions) unprotonated anions and the cations with prototype hydrogen bridges N^⊕H…︁N. The structures of both identically substituted R_nN (methylamine, trimethylamine, quinuclidine, diazabicyclooctane, and pyridine) as well as two-component cation species (quinuclidine…︁pyridine and diazabicyclooctane…︁pyridine) are reported and discussed. A Cambridge Structural Database search defines the area of charged N^⊕H…︁N interactions which can be correlated with both pK values and PM3 formation enthalpies. Additional information is provided by PM3 calculations based on the experimental structure coordinates. The charge distribution within the hydrogen bridges N^⊕H…︁N varies considerably with the individual proton donors N⁺H and proton acceptors N: Positive charges are highest at protonated quinuclidine and diazabicyclooctane centers and lowest at pyridine N acceptor centers.     

On the acidity of liquid and solid acid catalysts: Part 1. A thermodynamic point of view

The protonation equilibria of weak bases (B) in solid acids (HClO₄/SiO₂, CF₃SO₃H/SiO₂, H₂SO₄/SiO₂) were studied by UV spectroscopy and the results were compared to those obtained for analogous compounds in concentrated aqueous solutions of strong acids (HClO₄, CF₃SO₃H, H₂SO₄). The behaviour of B in liquid (L) and solid (S) phase was analysed by titration curves, log[BH⁺]/[B] ratios and thermodynamic pK _BH+ values. It has been shown that the proton transfer process acid → base (i.e., from (H+A^-)_(L,S) to (BH+A^-)_(L,S)} can be described by the relationship observed between the activity coefficient terms that are to be taken into account for acid–base equilibria occurring in nonideal systems ( – log(f _B f _B+/f _BH+)_(L,S)= -n _BA log(f _A–f _H+/f _HA)_(L,S)) and can be estimated by the n _BA values. Two “activity coefficient functions” (i.e., Mc(B) = – log(f _B f _B+/f _BH+)and Mc(s) = – log(f _A–f _H+/f _HA)) were used to describe, respectively, the equilibria of B and the equilibria of the acids in concentrated aqueous solutions and the meaning of terms “activity coefficient function” and “protonating ability of an acid” were discussed. The difference between “acidity functions”, determined for solutes (Ac(i)) and solvents (Ac(s)) in aqueous acids, and the H_x acidity functions, the latter developed for solutes in analogous media by the Hammett procedure, was also shown. This revised version was published online in July 2006 with corrections to the Cover Date.     

Application of critical state to uniaxial compaction

From the radial stress σ_R and the normal stress σ_A, measured continuously during uniaxial loading and unloading on three compactable (sodium chloride, polyethylene and tartaric acid) and two non-compactable (polypropylene and polystyrene plastics) materials, characteristic compaction profiles of (σ_A ? σ_R) versus (σ_A + σ_R) can be observed. The uniaxial loading stress pathways for both compactable and non-compactable materials validated the assumption that the Coulomb yield criterion, which is usually applicable for the shear testing of soils, can be applied to the uniaxial compression of particulate materials. In addition, the unloading stress profiles for the compactable materials produced two characteristic parameters: a normal stress value at zero shear (σ_A + σ_R)_o and a minimum shear stress value (σ_A ? σ_R)_min. Correlation of (σ_A + σ_R)_o and (σ_A ? σ_R)_min values with either the tensile strength f_c or the Vickers hardness number H_V from the resultant compacts showed a linear logarithmic relationship. No such relationship was found, however, with non-compactable materials.     

A new polyborate anion, [B7O9(OH)6]3−: Self assembly,XRD and thermal properties of s-fac-[Co(dien)2][B7O9(OH)6]·9H2O

The title compound, s-fac-[Co(dien)₂][B₇O₉(OH)₆]·9H₂O (1) (dien = HN(CH₂CH₂NH₂)₂), has been prepared as a crystalline solid in moderate yield (35%) from the reaction of B(OH)₃ with [Co(dien)₂][OH]₃ in aqueous solution (10:1 ratio). The structure contains a novel polyborate anion [B₇O₉(OH)₆]^3 − which is structurally based on the known ‘ribbon’ isomer of [B₇O₉(OH)₅]^2 −, with an additional [OH]⁻ group coordinated to a B atom in one of the outer boroxole rings. Compound 1 is formed by a self-assembly process in which the cation and anion mutually template themselves from equilibrium mixtures under reaction conditions. The [B₇O₉(OH)₆]^3 − anions are H-bonded to each other in layers with ‘cavities’ suitable for the [Co(dien]₂]^3 + complex. Three [B₇O₉(OH)₆]^3 − anions are in the secondary coordination sphere (via H-bonds) of each cation, with each anion H-bonded to three cations.     

3D supramolecular open-framework constructed by inorganic [B5O6(OH)4]− and organic [CH3COO]− anions

A borate compound [Ni(en)₃][B₅O₆(OH)₄][CH₃COO] (1) has been synthesized under mild hydrothermal conditions. The newly synthesized compound was characterized by single-crystal X-ray diffraction, elemental analysis and thermogravimetry. The three-dimensional (3D) supramolecular open-framework of compound 1 is constructed by inorganic [B₅O₆(OH)₄]⁻ building units and organic [CH₃COO]⁻ anions through hydrogen bonds, and the charge-balancing [Ni(en)₃]^2 + cations are located in 3D channels. It is very interesting that there exist two helical chains formed by [B₅O₆(OH)₄]⁻ building units and organic [CH₃COO]⁻ anions through hydrogen bonds in compound 1 along different axes. Magnetic measurement indicates that compound 1 exhibits paramagnetic behavior down to 4 K.     

SYNTHETIC INORGANIC ION-EXCHANGE MATERIALS. XXXXI. ION EXCHANGE EQUILIBRIA OF ALKALI METAL IONS/HYDROGEN IONS ON TIN(IV) ANTIMONATE

Ion exchange equilibria of alkali metal ions (Li⁺, Na⁺, K⁺,, Rb⁺, and Cs⁺)H⁺, systems have been studied in MNO-j-HNOj media with ionic strength of 0.1 at 30, 45 and 60 °C on tin(IV) antimonate as a cation exchanger. The ion exchange isotherms have been measured for both forward and backward reactions by the batch technique. The isotherms showed S-shaped curves for all exchange systems studied. The selectivity coefficients (logarithmic scale) vary with the equivalent fraction X_M of alkali metal ions in the exchanger and give two linear functions of X_M with a break point (X_M= 0.14, except 0.04 for Li⁺, /H⁺) indicating two different exchanging sites. The selectivity sequence, Na⁺, ? K⁺, ? Rb⁺, ? Cs⁺, ? ? Li, holds in the range of Xu= (0 - 0.04) and the sequence, Cs < Rb ⁺, ? K ⁺, ? Na ⁺, < Li ⁺, applies when X_M is higher than 0.14.

Hypothetical thermodynamic data on “zero loading” of the ion exchange reaction was evaluated.     

Electrochemical study of β-diketonatobis(triphenylphosphite)rhodium(I) complexes

The electrochemical behaviour of the series of ten [Rh(RCOCHCOR′)(P(OPh)₃)₂] complexes with R, R′ = CF₃, CF₃ (1), CF₃, CH₃ (2), CF₃, Ph (C₆H₅) (3), CF₃, Fc (ferrocenyl = (C₅H₅)Fe(C₅H₄)) (4), CH₃, Ph (5), CH₃, CH₃ (6), Ph, Ph (7), Fc, CH₃ (8), Fc, Ph (9) and Fc, Fc (10) were studied in acetonitrile containing 0.100 mol dm⁻³ tetra-n-butylammonium hexafluorophosphate as supporting electrolyte utilizing a glassy carbon working electrode. Results are consistent with Rh(I) being first oxidized in an electrochemically irreversible two-electron transfer process at peak anodic potentials ranging E_pa(Rh) = 0.124–0.881 V vs. Fc/Fc⁺. For the ferrocene-containing complexes (4), and (8)–(10) the rhodium oxidation was followed by the electrochemically reversible oxidation of the ferrocenyl group in a one-electron transfer process at a slightly more positive potential. Relationships were established between the electrochemical quantity E_pa(Rh) and kinetic parameter log k₂ as well the sum of experimental group electronegativities (Gordy Scale) of the R and R′ groups (χ_R + χ_R′), the Hammett σ values (σ_R + σ_R′) and the Lever ligand parameter E_L for the [Rh(RCOCHCOR′)(P(OPh)₃)₂] complexes: E_pa(Rh) (vs. Fc/Fc⁺/V) = 0.31 (χ_R + χ_R′)–1.09 = 0.56 (σ_R + σ_R′) + 0.28 = S_M (ΣE_L) + (I_M − 0.66 V) = −0.23 log k₂ − 0.03 (k₂ = second order rate constant for the oxidative addition of methyl iodide to rhodium). A profound shift of E_pa(Rh) to a more positive potential was observed for Rh(I) substrates containing β-diketonato ligands with increasing electronegative substituents R and R′. An exponential dependence of E_pa(Rh) on the pK_a of the β-diketone was obtained.