Estimation of the agglomeration structure for conductive particles and fiber‐filled high‐density polyethylene through dynamic rheological measurements

A study on the correlation between electrical percolation and viscoelastic percolation for carbon black (CB) and carbon fiber (CF) filled high‐density polyethylene (HDPE) conductive composites was carried out through an examination of the filler concentration (?) dependence of the volume resistivity (ρ) and dynamic viscoelastic functions. For CB/HDPE composites, when ? was higher than the modulus percolation threshold (?_G ～ 15 vol %), the dynamic storage modulus (G′) reached a plateau at low frequencies. The relationship between ρ and the normalized dynamic storage modulus (G_c^′/G_p^′, where G_c^′ and G_p^′ are the dynamic storage moduli of the composites and the polymer matrix, respectively) was studied. When ? approached a critical value (?_r), a characteristic change in G_c^′/G_p^′ appeared. The critical value (G_c^′/G^′_p)c was 9.80, and the corresponding ?_r value was 10 vol %. There also existed a ? dependence of the dynamic loss tangent (tan δ) and a peak in a plot of tan δ versus the frequency when ? approached a loss‐angle percolation (?_δ = 9 vol %). With parameter K substituted for A, a modified Kerner–Nielson equation was obtained and used to analyze the formation of the network structure. The viscoelastic percolation for CB/HDPE composites could be verified on the basis of the modified equation, whereas no similar percolation was found for CF/HDPE composites. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1199–1205, 2004     

Reentrant behavior of poly(vinyl alcohol)–borax semidilute aqueous solutions

 The reentrant behavior of Poly(vinyl alcohol) (PVA)–borax aqueous semidilute solutions with a PVA concentration of 20 g/l and borax concentrations varies from 0.0 to 0.20 M was investigated using dynamic light scattering (DLS) and dynamic viscoelastic measurements. Two (fast and slow modes) and three (fast, middle, and slow) relaxation modes of PVA semidilute aqueous solutions without and with the presence of borax, respectively, were observed from DLS measurements. The fast and middle relaxation modes were q ²-dependent (q is the scattering vector) characteristic of diffusive behavior; however, the slow modes were q ³-dependent, characteristic of intraparticle dynamics. The experimental results showed that the slow relaxation mode dominates the DLS relaxation. The DLS slow mode relaxation time, τ_s, and the viscoelastic modulus G′(ω) and G′′(ω) data had a similar trend and demonstrated reentrant behavior as the borax concentration was increased from 0.0 to 0.20 M, i.e. τ_s, G′(ω), and G′′(ω) fluctuated with increasing borax concentration. The excluded-volume effect of polymers, charge repulsion among borate ions bound on PVA molecules, and intermolecular cross-linking didiol–borate complexation caused an expansion of the polymer chain; however, the screening effect of free Na⁺ ions on the negative charge of the borate ions bound on PVA and intramolecular cross-linking didiol–borate complexation led to a shrinkage of the polymer chain. The reentrant behavior was the consequence of the balance between expansion and shrinkage of the PVA–borate complex. Received: 26 March 1999/Accepted in revised form: 3 September 1999     

Relationship between the positive temperature coefficient of resistivity and dynamic rheological behavior for carbon black‐filled high‐density polyethylene

Studies on the relationship between resistivity and dynamic rheological properties of carbon black‐filled high‐density polyethylene (CB/HDPE) composites were carried out. Change of resistivity ρ is associated with the dynamic modulus before the positive temperature coefficient/negative temperature coefficient (PTC/NTC) transition temperature. When the temperature approaches the melting point of HDPE, ρ increases rapidly with a decreasing modulus, corresponding to PTC transition. The resistivity‐dynamic viscoelasticity relationship in the PTC region can be divided into two parts in which the changes of ρ with storage modulus G′ and loss modulus G″ can be described by the scaling laws given by the critical storage modulus and loss modulus G′_c and G″_c; adjustable parameters ρ′_1c, ρ′_2c, ρ″_1c and ρ″_2c; and nonlinear exponents n and m, respectively. The accordance between the experimental data and the scaling functions of the dimensionless quantities (G′/G′_c ? 1) and (G″/G″_c ? 1) in the PTC transition region suggests that the ρ jump may be the result of a modulus‐induced percolation. G′_c and G″_c increase, but the four scaling resistivitis, ρ′_1c, ρ′_2c, ρ″_1c, and ρ″_2c, decrease with increasing CB concentration, implying that the microstructure change of the composites is the determinant factor for the PTC behavior and the resistivity‐dynamic modulus relationship. However, ρ′_2c and ρ″_2c exhibit no scaling dependence. It is suggested that a threshold concentration exists for the modulus of the composites on the basis of examining the plot of both G′_c and G″_c against CB concentration. The scaling laws G′ ～ Φ^x and G″ ～ Φ^y hold for the concentration dependence of the critical modulus when Φ > Φ_c and the estimated values of x and y are 1.10 ± 0.10 and 0.89 ± 0.29, respectively. The resistivity‐dynamic modulus can shift to form a master curve. The horizontal factors a_G′ and a_G″ and the vertical factors a′ and a″ are relevant to the concentration dependence of the dynamic modulus or PTC behavior. It is believed that the former would be involved in changing the mechanical microstructure formed by the complicated interaction of CB particle and polymer segments, and the latter would be involved in the overall changes of conducting a network during the PTC transition region. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 983–992, 2003     

Flocculation kinetics of an ochre suspension in salt(NaCl)-containing aqueous media in the presence of anionic and cationic acrylamide copolymers

The sedimentation kinetics of an ochre suspension in salt (NaCl)-containing aqueous media was studied in the presence of ionogenic (anionic, A, and cationic, C) acrylamide copolymers with high molecular weight (M > 2 × 10⁶) using a VT–0.5 torsion balance. The ionic strength of the dispersion medium varied in the wide range from 0.001 N to 0.4 N. The flocculation proceeded predominantly by a `bridge' mechanism, and the fraction of macromolecules inactive in the acts of floccule formation was significantly higher for C copolymer as compared with A copolymer. A drastic fall in the flocculating activities of A and C copolymers when passing from salt-free to salt-containing media is caused mainly by two following events: 1. The change in the conformational state of macromolecules, primarily, in their effective dimensions 2. The participation of a certain part of electrolyte in the formation and modification of an electrical double layer around disperse phase particles After introducing binary compositions of A and C flocculants into salt-containing media their resultant flocculating effect depends on the introduction mode of polymeric components. A strong difference in the magnitudes of the flocculating effect for A and C copolymers is observed in water. In the region of high ionic strengths (0.1–0.4 N) this difference becomes far less distinct. The flocculating activities of A and C copolymers were compared when introduced as the first (λ_A and λ_C) and the second (λ_A ^′ and λ_C ^′) additives. It was shown that λ_A/λ_A ^′>1 and λ_C/λ_C ^′>1. Such relationship between λ_A and λ_A ^′, λ_C and λ_C ^′ indicates that selective interactions between A and C copolymers play an essential role in the flocculation processes. The last statement was indirectly confirmed in the present work by the data of electrochemical and viscosimetric studies. When using C copolymer as the second additive in the region of low ionic strengths its main function undergoes reversal, and the copolymer begins to operate not as a flocculant, but as a stabilizer of disperse phase particles (λ_C< 0). Received: 14 April 2000 Accepted: 4 August 2000     

Dependence of the energy of surface-active substances/metal interaction on their ionization potentials. Evaluation of hydrophilicity of metal

The function Δ(ΔG _A ⁰), which is the difference of Gibbs energies characterizing surface-active substance (surfactant, SAS) adsorption at metal/solution and air/solution surfaces, has been introduced. The equation connecting the function Δ(ΔG _A ⁰) with SAS ionization potential has been obtained using the elementary theory of donor-acceptor interactions. Published experimental data on SAS adsorption at mercury, bismuth and gold have been used for Δ(ΔG _A ⁰) calculation. The dependence of Δ(ΔG _A ⁰) on ionization potentials can be described by an equation derived in this work. It has been demonstrated that the value of the hydrophilicity of gold is much higher than the values for mercury and bismuth. The lifetime of SAS molecules at a metal surface has been estimated. The question of the possibility of theoretica l estimation of standard energies ΔG _A ⁰ characterizing SAS adsorption at a metal/solution surface has been discussed. Received: 9 December 1996 / Accepted: 13 January 1997     

Theoretical studies on N-loss predissociation mechanisms of N2O+ (A?2Σ+) in Cs symmetry

The N-loss predissociation mechanisms of the A ²Σ⁺ (2 ² A′) state of N₂O⁺ to the first and second dissociation limits were studied in the C _s symmetry. The potential energy curves (PECs) and minimum energy crossing points (MECPs) for the C _s states of N₂O⁺ were calculated at the CAS levels. On the basis of our CAS calculation results (CASPT2 energetic results and CASSCF spin orbit couplings), we suggest two processes for N-loss predissociation mechanisms of A ²Σ⁺ (2 ² A′) to the first and second limits. The first two steps in the two processes are the same: A ²Σ⁺ passes through the 2 ² A′/1 ⁴ A″ MECP and then reaches the 1 ⁴ A″ (1 ⁴Σ⁻) PEC. The 2 ² A′/1 ⁴ A″ MECP has a bent geometry and is slightly higher in energy than the transition state along the 1 ⁴ A″ PEC. Our mechanisms are different from the previously suggested mechanisms (via 1 ⁴Π).     

Quenching of Li (2P) by H2: potential energy surfaces, conical intersection seam, and diabatic bases

The quenching of Li (1s ²2p; ²P) to Li (1s ²2s; ²S) by H₂ is considered using coupled-cluster and multireference configuration-interaction techniques. C _{2 v} (²A₁, ²B₂) and C _{∞ v} (²Π,²Σ⁺) sections of the 1²A^′ and 2²A^′ potential energy surfaces are determined. The C _{2 v} portion of the 1²A^′−2²A^′ seam of conical intersection is studied. Perhaps the most significant finding is a surprising trifurcation of this seam into a portion with only C _s symmetry and the aforementioned C _{2 v} portion. The adiabatic-to-diabatic state transformation is considered in the vicinity of the seam of conical intersection using both perturbation theory and the dipole moment operator. The ²B₂ section of the 2²A^′ potential energy surface exhibits an exciplex in the general vicinity of the seam of conical intersection. The ²Π section of the 2²A^′ potential energy surface possesses a global minimum lying 1.86kcal/mol below the Li (²P)+H₂ asymptote. A van der Waals-like minimum with C _{∞ v} symmetry was found on the 1²A^′ potential energy surface. Received: 14 August 1998 / Accepted: 20 August 1998 / Published online: 11 November 1998     

Salting-in behavior of isotropic and anisotropic aqueous hydroxypropylcellulose solutions

 Salts with large polarizable ions are capable of salting-in complex aqueous polymer solutions exhibiting microstructure, thereby inducing changes in the phase behavior and properties of the solutions. In this work, the dynamic rheological properties of isotropic and mesomor-phic hydroxypropylcellulose (HPC) in aqueous media have been investigated in the presence of one such salt, guanidine thiocyanate (GuSCN). Addition of this salt to isotropic aqueous HPC solutions is found to induce an increase in the magnitude of the elastic shear modulus (G′). At HPC concentrations above the isotropic→mesophase transition, however, addition of GuSCN results in a substantial reduction in G′ due to microstructural changes in the chiral nematic HPC mesophase. This reduction in G′ indicates that the microstructure of a water-soluble polymer exhibiting supramolecular organization can be tailored through salting-in, and is likewise expected to facilitate the commercial processing of HPC at high solids concentrations. Received: 4 June 1996 Accepted: 3 September 1996     

A Links‐Nodes‐Blobs Model for Conductive Polymer Composites

A Links‐Nodes‐Blobs (L‐N‐B) model, based on the fractal and percolation concepts, is used to study the electrically conductive mechanism of conductive filler loaded polymer composites. The change in the conductivity of polymer composites during the mixing process can be explained as the competition between the breakdown of filler aggregates and the diffusion of ingredients of matrix material and impurities onto the surface of the filler. The value of the fractal dimension μ, which is the exponent in the power‐law relationship of the electrical conductivity σ = σ₀·(ϕ – ϕ_c)^μ, is calculated as 1.88. This value is close to the values obtained directly from experiments or from other simulations. The positive temperature coefficient (PTC) behavior in the conductivity of composite material is also explained by this model as the breakdown of the conductive filler network. If the thermo‐expansion induced strain is greater than the apparent on‐set strain ε_onset = mQ + 2 G/2d G·ε_b of the L‐N‐B model, a strong PTC effect would happen.     

Quasi-thermodynamics of Viscous Flow of Electrolyte Solutions in Aqueous, Non-aqueous and Mixed Aqueous Solvents

Viscosity B-coefficients for cesium chloride and lithium sulfate in methanol + water mixtures at 25 and 35 °C are reported. A general treatment of the quasi-thermodynamics of viscous flow of electrolyte solutions is described. ΔG ₃ ^Θ (1→1′), the contribution made to the Gibbs energy of activation of the solution by the influence of the solute on the solvent, is a function of solute–solvent interactions only; but, ΔH ₃ ^Θ (1→1′) and ΔS ₃ ^Θ (1→1′) also reflect the solvent–solvent interactions. In aqueous solution all alkali-metal ions except Li⁺ are sterically unsaturated, having solvent co-ordination numbers n<n _max, the maximum allowed sterically. Such complexes exchange molecules with the solvent more readily than saturated ones and have energy–reaction co-ordinate diagrams in forms that explain the negative B or ΔG ₃ ^Θ (1→1′) values found in aqueous solution. Saturated complexes are the norm in non-aqueous solvents, and the ΔG ₃ ^Θ (1→1′) values are determined mainly by the secondary solvation. Behavior in mixed solvents reflects the transition from aqueous to non-aqueous behavior across the range of solvent composition.     

Synthesis,crystal structure,and thermal decomposition kinetics of complex [Nd(BA)<Subscript>3</Subscript>bipy]<Subscript>2</Subscript>

The complex of [Nd(BA)₃bipy]₂ (BA = benzoic acid; bipy = 2,2′-bipyridine) has been synthesized and characterized by elemental analysis, IR spectra, single crystal X-ray diffraction, and TG/DTG techniques. The crystal is monoclinic with space group P2(1)/n. The two–eight coordinated Nd³⁺ ions are linked together by four bridged BA ligands and each Nd³⁺ ion is further bonded to one chelated bidentate BA ligand and one 2,2′-bipyridine molecule. The thermal decomposition process of the title complex was discussed by TG/DTG and IR techniques. The non-isothermal kinetics was investigated by using double equal-double step method. The kinetic equation for the first stage can be expressed as dα/dt = A exp(−E/RT)(1 − α). The thermodynamic parameters (ΔH ^≠, ΔG ^≠, and ΔS ^≠) and kinetic parameters (activation energy E and pre-exponential factor A) were also calculated.     

Dynamic scaling for gelation of a thermosensitive chitosan-β-glycerophosphate hydrogel

This paper investigates the thermal gelation of a chitosan-β-glycerophosphate system using rheometry. The gelation, performed for two polymer concentrations, was achieved in isothermal conditions to examine the effect of various temperatures (between 35 and 65 °C) on the sol-gel transition. The oscillatory shear data was used to verify the scaling behavior (G′ ~ G″ ~ ω ⁿ ) at the gel point, and the power-law index n was found to be dependent to some extent on chitosan concentration and temperature. The solutions zero shear viscosity (η ₀) and the gels low frequency modulus (G _e) were analyzed in terms of the relative distance to gelation time (ɛ). The two properties showed power–law relationships with ɛ, i.e., η ₀ ~ ɛ ^−s and G _e ~ ɛ ^z, and the indexes slightly increased with temperature. The dynamic scaling theory predicts a relationship between the indexes, i.e., n  =  z/(z  +  s), and this was in reasonably good agreement with the experimental findings.     

Effect of unsaturated hydroxyl-fatty acid modified nano-CaCO3 on the morphological and rheological behavior of PP

A modified nano-calcium carbonate (R-CCR) was prepared by coating a layer of unsaturated hydroxylfatty acid on the surface of CCR powders using a solid state method; the latter were commercial nano-CaCO₃ modified with stearic acid. FTIR studies indicate that the modifier is combined on the surface of CaCO₃. PP/EPDM/nano-CaCO₃ ternary composites were prepared by a melt-mixing method. SEM and TEM were utilized to examine the morphology of the composites. The tensile fractured surface of PP/EPDM/R-CCR showed a fibroid morphology and large-scale yield deformation. The impact fractured surface showed that the amount of cavities in the PP/EPDM/R-CCR system was increased, however their size diminished obviously. R-CCR particles were dispersed uniformly in the PP matrix, and their compatibility was distinctly improved as compared to CCR when the amount of R-CCR was 15 h⁻¹. The tensile strength remained nearly constant (reduced from 27.6 MPa to 27.5 MPa), while the impact strength increased from 9.6 kJ/m² to 15.4 kJ/m² as CCR was replaced by R-CCR. Meanwhile, the bending strength and bending modulus also increased correspondingly. Furthermore, the impact strength of PP/EPDM/R-CCR was maintained at a high level (15.4 kJ/m²), which was more than the sum of that of PP/EPDM and PP/R-CCR (6.6 kJ/m² and 6.1 kJ/m² respectively). This indicates that the R-CCR and EPDM have a significant synergistic toughening effect on PP while maintaining the strength and modulus of virgin PP. Both the storage modulus G′ and loss modulus G″ of PP/EPDM and PP/EPDM/R-CCR composites increase with increasing frequency, but the values of G′ and G″ of the tertiary composite are relatively higher than those of the binary system. The loss factor and viscosity decrease with increasing frequency, but there is little difference between tertiary and binary composites. The apparent viscosity η of the tertiary system containing R-CCR is lower than that of the tertiary system containing CCR and virgin PP. The viscosity of the composites sig-nificantly decreases with increasing shear rate. The mea-sured mechanical properties of the composites indicate that replacing CCR with R-CCR for binary composites could simultaneously enhance the toughness and strength of PP. __________ Translated from Acta Polymerica Sinica, 2008, 4 (in Chinese)     

Studies of the interaction between daidzein and 3′-daidzein sulfonic sodium with bovine serum albumin by spectroscopic methods

The interaction between daidzein and 3′-daidzein sulfonic sodium with bovine serum albumin (BSA) in physiological buffer (pH = 7.4) is investigated by fluorescence quenching technique and UV/vis absorption spectra. The results reveal that both daidzein and 3′-daidzein sulfonic sodium could strongly quench the intrinsic fluorescence of BSA. The quenching mechanism of both the daidzein and 3′-daidzein sulfonic sodium for BSA is static quenching procedure. The apparent binding constants K _a and number of binding sites n of daidzein and 3′-daidzein sulfonic sodium with BSA are obtained by fluorescence quenching method. The thermodynamic parameters, enthalpy change (Δ_r H ^m ), and entropy change (Δ_r S ^m ), are calculated, respectively, which indicate that the interaction of daidzein with BSA is driven mainly by hydrogen bonding and van der Waals, and 3′-daidzein sulfonic sodium with BSA is driven mainly by hydrophobic forces. The distance r between BSA with daidzein and 3′-daidzein sulfonic sodium are calculated to be 4.02 nm and 3.08 nm, respectively, based on F?rster’s non-radiative energy transfer theory. The results of synchronous fluorescence spectra show that binding of daidzein and 3′-daidzein sulfonic sodium with BSA cannot induce conformational changes in BSA.     

Reciprocity relation in scattering by media subjected to an external magnetic field

Summary Krishnan's reciprocity theorem in colloid optics,ϱ _u=1+l/ϱ_h/1+1/ϱ _v is generalised for the case when the scattering medium is subjected to an external orienting field. It is shown theoretically that a general relation of the typeI _B ^A =I′ _A ^B results in this case, whereI _B ^A is the intensity of the component of the scattered light having its electric vector inclined at an angleB to the vertical with the incident light polarised at an angleA to the vertical, the external field direction being parallel to the incident beam.I′ _A ^B is the corresponding intensity with the magnetic field parallel of the scattered ray. Experimental verification of the above generalisation is also given.

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Zusammenfassung Krishnans Reziprozit?tstheoremϱ _u=1+1/ϱ _h/1+1/ϱ _v wird für den Fall verallgemeinert, da\ das streuende Medium einem ?u\eren orientierenden Feld unterliegt. Es l?\t sich theoretisch zeigen, da\ in diesem Fall eine allgemeine Beziehung des TypsI _B ^A =I′ _A ^B resultiert, in derI _B ^A die Intensit?t der Komponente des Streulichts mit dem elektrischen Vektor um den WinkelB zur Vertikalen geneigt bei einfallendem Licht um einen WinkelA zur Vertikalen polarisiert angibt, und das ?u\ere Feld parallel zum einfallenden Strahl liegt.I′ _A ^B ist die entsprechende Intensit?t mit dem Magnetfeld parallel zum gestreuten Strahl. Eine experimentelle Best?tigung der genannten Verallgemeinerung wird gegeben.

     

Hyperbranched copolymers made from A2, B2 and BB′2type monomers (iv)

The new approach for synthesis of hyperbranched polymers from commercially available A₂ and type monomers was extended to synthesize hyperbranched copolymers. In this work, hyperbranched copoly(sulfone-amine) was prepared by copolymerization of divinyl sulfone (A₂) with 4,4′-trimethylenedipiperidine (B₂) and N-ethylethylenediamine (BB’₂). During the reaction, secondary-amino groups of B₂ and BB’₂ monomers react rapidly with vinyl groups of A₂ monomers within 35 s, generating a type of intermediate containing one vinyl group and two reactive hydrogen atoms. Now the intermediates can be regarded as a new type monomer, which further polymerizes to form hyperbranched copoly(sulfone-amine). The polymerization mechanism was investigated with FTIR and LC-MSD. The degree of branching (DB) of hyperbranched copolymers increased with decreasing the ratio of 4, 4′-trimethylenedipiperidine to N-ethylethylenediamine, so DB can be controlled. When the initial mole ratio of B₂ to BB′₂was equal to or higher than four,r≥4, resulted copolymers were semi-crystalline, while copolymers withr3 were amorphous.     

Crystal Structure of infin; 2[Cu2I2(μ-4-4′-bipyridine)] and Investigations on the Thermal Decomposition of CuX-4,4′-bipyridine Coordination Polymers

Summary.  The inorganic-organic coordination polymer _infin; ²[Cu₂I₂(μ-4-4′-bipyridine)] was prepared by the reaction of Cu(I)I and 4,4^′-bipyridine in acetonitrile. Its structure consists of staircase-like CuX double chains which are connected to sheets by the 4,4^′-bipyridine ligands. The thermal decomposition of the corresponding 1:1 copper(I) halide-4,4^′-bipyridine compounds _infin; ²[CuX(μ-4-4′-bipyridine)] (X = Cl, Br, I) was investigated using simultaneous difference thermal analysis and thermogravimetry (DTA-TG), thermomicroscopy, and temperature resolved X-ray powder diffraction in air or argon. Upon heating _infin; ²[CuX(μ-4-4′-bipyridine)], several changes in sample mass are observed which correspond to a stepwise loss of the organic ligands. Temperature-resolved X-ray powder diffraction proves that _infin; ²[CuX(μ-4-4′-bipyridine)] transforms to _infin; ²[Cu₂ X ₂(μ-4-4′-bipyridine)] during the decomposition; the latter looses the remaining ligands when heated further, forming the corresponding copper(I)halides. When the experiments were performed under an argon atmosphere, the 2:1 coordination polymers were obtained as phase-pure compounds. Received March 1, 2001. Accepted April 11, 2001     

Crystal Structure of infin;2[Cu2I2(μ-4-4′-bipyridine)] and Investigations on the Thermal Decomposition of Cu X -4,4′-bipyridine Coordination Polymers

 The inorganic-organic coordination polymer _infin; ²[Cu₂I₂(μ-4-4′-bipyridine)] was prepared by the reaction of Cu(I)I and 4,4^′-bipyridine in acetonitrile. Its structure consists of staircase-like CuX double chains which are connected to sheets by the 4,4^′-bipyridine ligands. The thermal decomposition of the corresponding 1:1 copper(I) halide-4,4^′-bipyridine compounds _infin; ²[CuX(μ-4-4′-bipyridine)] (X = Cl, Br, I) was investigated using simultaneous difference thermal analysis and thermogravimetry (DTA-TG), thermomicroscopy, and temperature resolved X-ray powder diffraction in air or argon. Upon heating _infin; ²[CuX(μ-4-4′-bipyridine)], several changes in sample mass are observed which correspond to a stepwise loss of the organic ligands. Temperature-resolved X-ray powder diffraction proves that _infin; ²[CuX(μ-4-4′-bipyridine)] transforms to _infin; ²[Cu₂ X ₂(μ-4-4′-bipyridine)] during the decomposition; the latter looses the remaining ligands when heated further, forming the corresponding copper(I)halides. When the experiments were performed under an argon atmosphere, the 2:1 coordination polymers were obtained as phase-pure compounds.     

Voltammetry of electroactive liquid redox systems: anion insertion and chemical reactions in microdroplets of para-tetrakis(6-methoxyhexyl) phenylenediamine, para- and meta-tetrahexylphenylenediamine

The effect of the structure of the organic precursor molecule on the electroinsertion of anions and on the formation of materials in the ionic liquid state is compared for three compounds, para-N, N, N′, N′-tetrahexylphenylenediamine (p-THPD), meta-N, N, N′, N′-tetrahexylphenylene diamine (m-THPD), and para-N, N, N′, N′-tetrakis(6-methoxyhexyl)phenylenediamine (p-TMHPD), by characterising their condensed phase voltammetric properties in aqueous media. The electrochemically driven anion insertion in p-THPD and p-TMHPD in the presence of ClO₄ ⁻, F⁻, Cl⁻, Br⁻, I⁻, and SO₄ ²⁻ is shown to be extremely sensitive to structure. The introduction of the methoxy end groups in p-TMHPD causes (1) a considerable shift to more negative electroinsertion potentials, (2) a less stable response which upon continuous cycling decreases, and (3) considerably lower anion selectivity. For the insertion of sulfate, only p-TMHPD yields an electrochemical response which is shown to be consistent with insertion of the dianion SO₄ ²⁻. The electrochemical oxidation of a deposit of m-THPD is accompanied by anion insertion and a chemical reaction step in an EC-type electrochemical process. The product of the chemical step is electrochemically active and results in a new reversible electroinsertion process. Starting materials and products of the microdroplet reactions are characterised by Maldi-TOF mass spectrometry and a reaction mechanism based on condensed phase polymerisation is proposed. Received: 15 November 1999 / Accepted: 2 December 1999     

Syntheses and characterization of three hybrid materials based on polymeric copper complexes and saturated Keggin polyoxoanions

Three novel heteropolytungstates, [Cu(phen)₂]₄[α-SiW₁₂O₄₀] (1), [Cu₄(4,4′-bpy)₃(2,2′-bpy)₄][α-SiW₁₂O₄₀] · H₂O (2) and [Cu(4,4′-bpy)(4,4′-Hbpy)_0.5]₂[PW₁₂O₄₀] (3) (phen = 1,10-phenanthroline, 4,4′-bpy = 4,4′-bipyridine, 2,2′-bpy = 2,2′-bipyridine), have been synthesized and characterized by elemental analyses, IR, TG analyses and single-crystal X-ray diffraction. Compound (1) exhibits interesting chiral layer constructed from interperpendicular helical chains running along a crystallographic 2₁ axis in the c and a directions. Furthermore, the chiral layers are connected by the [α-SiW₁₂O₄₀]⁴⁻ anions via hydrogen bonding interactions to form a 3D superamolecular structure. The [Cu₄(4,4′-bpy)₃(2,2′-bpy)₄]⁴⁺ coordinated complexes in compound (2) are packed together via the aromatic π–π stacking interactions and exhibit an interesting 3D sandglasslike “host” network with 1D channels, in which [α-SiW₁₂O₄₀]⁴⁻ anions “guests” reside. Compound (3) has a unique 2D superamolecular network, which is composed of cationic Cu^I coordination polymer chains and discrete [PW₁₂O₄₀]³⁻ polyoxoanions as linkers. It is noteworthy that the monprotonated 4,4′-bpy ligands of (3) act as arms and connect the adjacent 2D network, generating a 3D interpenetrating superamolecular structure.