Effect of chain aggregation on the conductivity and ESR spectra of polyaniline

Solutions of polyaniline in m-cresol with and without camphorsulfonic acid (CSA), as well as films cast from these solutions were studied by ESR spectroscopy at 133–423 K and by optical spectroscopy in the range λ = 350–1100 nm. An analysis of the optical and ESR spectra shows that in the solutions and films without CSA polyaniline is fully doped but the conductivity of these films is low (∼10⁻⁸ S cm⁻¹; cf. 100 S cm⁻¹ for the films with CSA). Compared with the CSA-containing samples, the samples without CSA are characterized by broader ESR lines and higher contribution of the Curie spins to the magnetic susceptibility. These facts indicate a weak aggregation of polyaniline chains without CSA, which leads to low conductivity. A formula was proposed, which describes the temperature dependence of the polyaniline ESR linewidth and allows the interchain distance and the mobility of electrons moving along polymer chains to be determined. The conductivity of polyaniline films is affected by moderate heating (363–388 K) of the films and solutions from which the films were cast. It was found that the interchain distances correlate with the conductivity of the films and with the broadening of their ESR lines caused by the effect of O₂. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2701–2711, December, 2005.     

Nature of paramagnetic centers in polyaniline as studied by SQUID magnetometry

The temperature and field dependences of the magnetic moment of polyaniline powder doped by m-cresol were measured by SQUID magnetometry in the temperature range 2–300 K at 1000 Oe and in the range 0–50000 Oe at 2 K, respectively. The field dependence is not described by the Brillouin function for spin 1/2, as is expected in the framework of a commonly accepted “metallic” model. Both dependences are quite correctly described by a “triplet” model using a distribution of singlet-triplet splitting (E) with the density distribution function having a narrow peak near E = 0.     

On the triplet nature of paramagnetic centers in conducting polymers

Temperature dependences of the magnetic susceptibility of solutions and powders of polyaniline synthesized by oxidative polymerization using two methods were measured by ESR in the temperature range from 123 to 423 K. The dependences observed can be described by the integral of susceptibility of the polymer fragments in the triplet state over the singlet—triplet splitting from E ₁ to E ₂ with constant weight. The susceptibility of the fragments was accepted to obey the Bleaney—Bowers equation. The most part of the experimental dependences can be presented as the sum of the temperature-independent susceptibility and the susceptibility obeying the Curie law. The both susceptibilities are described in a single manner at E ₁ < 0. In some cases, the comparison of the calculated and experimental dependences makes it possible to determine the length of the fragments L. The conditions of polymer synthesis, heating, and water vapors affect the E ₁ and E ₂ values. A similar analysis can be applied to other conducting polymers. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 316–321, February, 2008.     

A new mechanism of the dioxygen effect on ESR spectra of polyaniline

The effect of dioxygen on the ESR spectra of powders of emeraldine salts at 170–230 K was found to depend on the time of storing of the samples at a specific temperature. The kinetics of changes in the ESR spectra reflects the conformational mobility of the polyaniline chains and its supramolecular structure. A new mechanism of the dioxygen effect on the ESR spectra of polyaniline at 50–100 K associated with the condensation of dioxygen in polyaniline pores was proposed.     

Effect of dioxygen on ESR spectra of polyaniline

The effect of dioxygen on the width of ESR lines of powders and films of polyaniline was studied at 15–300 K. It was found that the line broadening can decrease or increase, which corresponds to strong or weak exchange, respectively. For dry polyaniline powders and films, maxdimum broadening was observed at 240 K. The findings were explained by spin exchange during collisions of a mobile polaron with immobile O₂ molecules bound to the polymer. The values of exchange interaction between the O₂ molecule and the polaron and the mobility of the polarons along the polymer chain were found. The mobility of polarons along the polymer chains decreases in the presence of H₂O, and dioxygen predominantly adds to the imine N atom. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2293–2297, December, 1999.     

Photochemical synthesis and ESR spectra of quintet meta-phenylenedinitrenes

Relationships between the molecular structures and zero-field splitting parameters of quintet m-phenylenedinitrenes formed during the photolysis of 1,3-diazidobenzenes in 2-methyltetrahydrofuran solutions frozen at 77 K were studied by ESR spectroscopy and B3LYP/6-31G* calculations. Simulations of the W₋₂/W₋₁, W₊₂/W₊₁, W₋₁/W₀, W₊₁/W₀, and W₊₂/W₀ (Δm _s = 2) transitions were performed for the first time and all signals in the ESR spectra of quintet m-phenylenedinitrenes were unambiguously assigned. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1085–1089, July, 2006.     

Study of the 1A1?5T2 spin transition in mix-ligand complexes of iron(II) hexafluorosilicate with 1,2,4-triazole and 4-amino-1,2,4-triazole

Synthesis procedures for mix-ligand complexes with a composition of Fe(Htrz)_3(1-x)(NH₂trz)_3x SiF₆ · mH₂O, 0 ≤ x ≤ 1, m=1,2 are developed. Solid phases are isolated from water-ethanol solutions and studied by X-ray phase analysis, the method of static magnetic susceptibility (temperature range of 100 K to 400 K), IR and M?ssbauer spectroscopy (at 200 K and 298 K). The temperatures of direct and inverse transitions are shown to depend on the complex composition.     

SQUID and ESR study of triplet paramagnetic centers in polyaniline

Temperature and field dependences of magnetic moments of powders of the polyaniline base and polyaniline doped with acid HClO₄ were measured by SQUID. The temperature dependences of the susceptibility were studied by ESR. A comparison of the susceptibilities determined by SQUID and ESR shows that a part of the susceptibility is not detected by ESR. This part is temperature-independent and, perhaps, is due to the Van Vleck paramagnetism. According to our and earlier published data for polyaniline and polypyrrole, the field dependences at helium temperatures are often characterized by the Brillouin function with S = 1, which cannot be explained in terms of the commonly accepted ??metallic?? model that predicts S = 1/2. It was established in this study that the field and temperature dependences can be explained in terms of the ??triplet?? model, and the absolute values of the mole moment are well simulated, i.e., not only the shapes of the dependences but also the values of the moment at different fields and temperatures.     

Molar heat capacity and thermodynamic properties of 1,2-cyclohexane dicarboxylic anhydride [C8H10O3]

The molar heat capacity C _p,m of 1,2-cyclohexane dicarboxylic anhydride was measured in the temperature range from T=80 to 390 K with a small sample automated adiabatic calorimeter. The melting point T _m, the molar enthalpy Δ_fus H _m and the entropy Δ_fus S _m of fusion for the compound were determined to be 303.80 K, 14.71 kJ mol⁻¹ and 48.43 J K⁻¹ mol⁻¹, respectively. The thermodynamic functions [H _T-H _273.15] and [S _T-S _273.15] were derived in the temperature range from T=80 to 385 K with temperature interval of 5 K. The thermal stability of the compound was investigated by differential scanning calorimeter (DSC) and thermogravimetry (TG), when the process of the mass-loss was due to the evaporation, instead of its thermal decomposition.     

The thermodynamic properties of S-lactic acid

The enthalpies of combustion and formation of S-lactic acid at 298.15 K, Δ_c H _m^o(cr.) = −1337.9 ± 0.8 and Δ_f H _m^o(cr.) = −700.1 ± 0.9 kJ/mol, were determined by calorimetry. The temperature dependence of acid vapor pressure was studied by the transpiration method, and the enthalpy of its vaporization was obtained, Δ_vap H ^o(298.15 K) = 69.1 ± 1.0 kJ/mol. The temperature and enthalpy of fusion, T _m (330.4 K) and Δ_m H ^o(298.15 K) = 14.7 ± 0.2 kJ/mol, were determined by differential scanning calorimetry. The enthalpy of formation of the acid in the gas phase was obtained. Ab initio methods were used to perform a conformational analysis of the acid, calculate fundamental vibration frequencies, moments of inertia, and total and relative energies of the stablest conformers. Thermodynamic properties were calculated in the ideal gas state over the temperature range 0–1500 K. A thermodynamic analysis of mutual transformation processes (the formation of SS- and RS(meso)-lactides from S-lactic acid and the racemization of these lactides) and the formation of poly-(RS)-lactide from S-lactic acid and SS- and RS(meso)-lactides was performed.     

Thermodynamic investigation of room temperature ionic liquid

The molar heat capacities of the room temperature ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborate (BMIBF₄) were measured by an adiabatic calorimeter in temperature range from 80 to 390 K. The dependence of the molar heat capacity on temperature is given as a function of the reduced temperature X by polynomial equations, C _P,m (J K^–1 mol^–1)= 195.55+47.230 X–3.1533 X ²+4.0733 X ³+3.9126 X ⁴ [X=(T–125.5)/45.5] for the solid phase (80~171 K), and C _P,m (J K^–1 mol^–1)= 378.62+43.929 X+16.456 X ²–4.6684 X ³–5.5876 X ⁴ [X=(T–285.5)/104.5] for the liquid phase (181~390 K), respectively. According to the polynomial equations and thermodynamic relationship, the values of thermodynamic function of the BMIBF₄ relative to 298.15 K were calculated in temperature range from 80 to 390 K with an interval of 5 K. The glass translation of BMIBF₄ was observed at 176.24 K. Using oxygen-bomb combustion calorimeter, the molar enthalpy of combustion of BMIBF₄ was determined to be Δ_c H _m ^o= – 5335±17 kJ mol^–1. The standard molar enthalpy of formation of BMIBF₄ was evaluated to be Δ_f H _m ^o= –1221.8±4.0 kJ mol^–1 at T=298.150±0.001 K.     

Preparation and characterization of anion-cation surfactants modified montmorillonite

The low-temperature molar heat capacities of CoPc and CoTMPP were measured by temperature modulated differential scanning calorimetry (TMDSC) over the temperature range from 223 to 413 K for the first time. No phase transition or thermal anomaly was observed in the experimental temperature range for CoPc. However, a structural change was found to be nonreversible for CoTMPP in the temperature range of 368–403 K, which was further validated by the results of IR and XRD. The molar enthalpy ΔH _m and entropy ΔS _m of phase transition of the CoTMPP were determined to be 3.301 kJ mol⁻¹ and 8.596 J K⁻¹ mol⁻¹, respectively. The thermodynamic parameters of CoPc and CoTMPP such as entropy and enthalpy relative to reference temperature 298.15 K were derived based on the above molar heat capacity data. Moreover, the thermal stability of these two compounds was further investigated through TG measurements. Three steps of mass loss were observed in the TG curve for CoPc and five steps for CoTMPP.     

Guest—host complexes of spin-labeled indoles with cyclodextrins in the solid phase: an esr study

Inclusion complexes of spin-labeled pyrrolidine-(1) and piperidine-containing (2) indole derivatives with β-cyclodextrin and γ-cyclodextrin (CD) were prepared in the solid phase and studied by ESR in a wide temperature interval. For all complexes and free spin probes in solvents of different polarity, local environment polarities of the NO group of the guest molecules were determined from the outer extrema separations in the ESR spectra measured at 77 K. From analysis of the Saturation Transfer (ST) ESR spectra and temperature dependences of linear ESR spectra of the complexes it follows that both guest molecules in γ-CD undergo rapid librations. The libration amplitude of the p-orbit axis of the NO group in molecule 2 increases with temperature and reaches about 16° at 333 K. The ESR lineshape of the β-CD complexes depends on the spin probe/β-CD molar ratio (ρ) even at ρ < 0.01. Lineshape analysis of the spectra recorded at different ρ showed that they consist of two components, one of them corresponding to strong spin-spin interaction between guest molecules and the other corresponding to almost absence of this interaction. The spectral components can be attributed to microphases of the complexes and to isolated complexes in the β-CD matrix, respectively. Simulation of the ST ESR and linear ESR spectra of the magnetically diluted complexes showed that the guest motion inside the CD cavity is better described by rotational jumps rather than Brownian diffusion in an orientation potential. In the temperature range 238—333 K, the rotational frequencies of 1 and 2 are in intervals 1.8·10⁷−6·10⁷ s⁻¹ and 4·10⁷⁻¹.3·10⁸ s⁻¹, respectively. The rotation occurs over the whole solid angle. Significant differences in the character of molecular dynamics in the γ-CD and β-CD complexes can be explained by different stoichiometry, namely, 1: 1 for the former and 2: 1 for the latter and by different orientation of guest molecules in the complexes. In both cyclodextrins the rotational mobility of molecules 2 is higher than that of 1 owing to intramolecular conformational transitions in the piperidine ring of 2 and steric hindrances produced by the methyl group in 1. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 233—241, February, 2006.     

Heat capacities and thermodynamic properties of 2-benzoylpyridine (C12H9NO)

The heat capacities of 2-benzoylpyridine were measured with an automated adiabatic calorimeter over the temperature range from 80 to 340 K. The melting point, molar enthalpy, Δ_fusH^m, and entropy, Δ_fusS^m, of fusion of this compound were determined to be 316.49±0.04 K, 20.91±0.03 kJ mol^–1 and 66.07±0.05 J mol^–1 K^–1, respectively. The purity of the compound was calculated to be 99.60 mol% by using the fractional melting technique. The thermodynamic functions (H_T–H_298.15) and (S_T–S_298.15) were calculated based on the heat capacity measurements in the temperature range of 80–340 K with an interval of 5 K. The thermal properties of the compound were further investigated by differential scanning calorimetry (DSC). From the DSC curve, the temperature corresponding to the maximum evaporation rate, the molar enthalpy and entropy of evaporation were determined to be 556.3±0.1 K, 51.3±0.2 kJ mol^–1 and 92.2±0.4 J K^–1 mol^–1, respectively, under the experimental conditions.     

Thermodynamic investigation of several natural polyols (II)

The low-temperature heat capacity C _p,m of sorbitol was precisely measured in the temperature range from 80 to 390 K by means of a small sample automated adiabatic calorimeter. A solid-liquid phase transition was found at T=369.157 K from the experimental C _p-T curve. The dependence of heat capacity on the temperature was fitted to the following polynomial equations with least square method. In the temperature range of 80 to 355 K, C _p,m/J K⁻¹ mol⁻¹=170.17+157.75x+128.03x ²-146.44x ³-335.66x ⁴+177.71x ⁵+306.15x ⁶, x= [(T/K)−217.5]/137.5. In the temperature range of 375 to 390 K, C _p,m/J K⁻¹ mol⁻¹=518.13+3.2819x, x=[(T/K)-382.5]/7.5. The molar enthalpy and entropy of this transition were determined to be 30.35±0.15 kJ mol⁻¹ and 82.22±0.41 J K⁻¹ mol⁻¹ respectively. The thermodynamic functions [H _T-H _298.15] and [S _T-S 298.15], were derived from the heat capacity data in the temperature range of 80 to 390 K with an interval of 5 K. DSC and TG measurements were performed to study the thermostability of the compound. The results were in agreement with those obtained from heat capacity measurements.     

Thermodynamic investigation of room temperature ionic liquid

The molar heat capacities of the room temperature ionic liquid 1-butylpyridinium tetrafluoroborate (BPBF₄) were measured by an adiabatic calorimeter in temperature range from 80 to 390 K. The dependence of the molar heat capacity on temperature is given as a function of the reduced temperature X by polynomial equations, C _p,m [J K⁻¹ mol⁻¹]=181.43+51.297X −4.7816X ²−1.9734X ³+8.1048X ⁴+11.108X ⁵ [X=(T−135)/55] for the solid phase (80–190 K), C _p,m [J K⁻¹ mol⁻¹]= 349.96+25.106X+9.1320X ²+19.368X ³+2.23X ⁴−8.8201X ⁵ [X=(T−225)/27] for the glass state (198–252 K), and C _p,m[J K⁻¹ mol⁻¹]= 402.40+21.982X−3.0304X ²+3.6514X ³+3.4585X ⁴ [X=(T−338)/52] for the liquid phase (286–390 K), respectively. According to the polynomial equations and thermodynamic relationship, the values of thermodynamic function of the BPBF₄ relative to 298.15 K were calculated in temperature range from 80 to 390 K with an interval of 5 K. The glass transition of BPBF₄ was observed at 194.09 K, the enthalpy and entropy of the glass transition were determined to be ΔH _g=2.157 kJ mol⁻¹ and ΔS _g=11.12 J K⁻¹ mol⁻¹, respectively. The result showed that the melting point of the BPBF₄ is 279.79 K, the enthalpy and entropy of phase transition were calculated to be ΔH _m = 8.453 kJ mol⁻¹ and ΔS _m=30.21 J K⁻¹ mol⁻¹. Using oxygen-bomb combustion calorimeter, the molar enthalpy of combustion of BPBF₄ was determined to be Δ_c H _m⁰ = −5451±3 kJ mol⁻¹. The standard molar enthalpy of formation of BPBF₄ was evaluated to be Δ_f H _m⁰ = −1356.3±0.8 kJ mol⁻¹ at T=298.150±0.001 K.     

Alkylation of m-cresol with methanol and 2-propanol over calcined magnesium-aluminium hydrotalcites

Magnesium-aluminium hydrotalcites (MgAl-HTs) with Mg/Al atomic ratio 2,3 and 4 were synthesized bythe coprecipitation method. Vapour phase alkylation of m-cresol with methanol was carried out over these samples calcined at 723K in the temperature range 523–723K at atmospheric pressure. A mixture of O- and C- alkylated products, namely, 3-methyl anisole (3MA), 2,5- and 2,3-dimethylphenols (DMP) and 2,3,6-trimethylphenol (2,3,6-TMP) were obtained. The selectivity of these products depends on the m-cresol/methanol feed ratio, temperature and contact times. The catalytic activity of these catalysts are in the order MgAl 3.0-CHT>MgAl 2.0-CHT>MgAl 4.0-CHT. MgAl 3.0-CHT showed ∼30% selectivity for 2,5-DMP and 40% selectivity for 2,3,6-TMP with ∼40% conversion at 623K or ∼70% conversion at 723K. The alkylation of m-cresol with 2-propanol over MgAl 3.0-CHT at 673K offered nearly 80% selectivity towards thymol with nearly 40% m-cresol conversion.     

Low-temperature heat capacities and thermodynamic properties of 2,2-dimethyl-1,3-propanediol

The molar heat capacities C _p,m of 2,2-dimethyl-1,3-propanediol were measured in the temperature range from 78 to 410 K by means of a small sample automated adiabatic calorimeter. A solid-solid and a solid-liquid phase transitions were found at T-314.304 and 402.402 K, respectively, from the experimental C _p-T curve. The molar enthalpies and entropies of these transitions were determined to be 14.78 kJ mol⁻¹, 47.01 J K⁻¹ mol⁻ for the solid-solid transition and 7.518 kJ mol⁻¹, 18.68 J K⁻¹ mol⁻¹ for the solid-liquid transition, respectively. The dependence of heat capacity on the temperature was fitted to the following polynomial equations with least square method. In the temperature range of 80 to 310 K, C _p,m/(J K⁻¹ mol⁻¹)=117.72+58.8022x+3.0964x ²+6.87363x ³−13.922x ⁴+9.8889x ⁵+16.195x ⁶; x=[(T/K)−195]/115. In the temperature range of 325 to 395 K, C _p,m/(J K⁻¹ mol⁻¹)=290.74+22.767x−0.6247x ²−0.8716x ³−4.0159x ⁴−0.2878x ⁵+1.7244x ⁶; x=[(T/K)−360]/35. The thermodynamic functions H _T−H _298.15 and S _T−S _298.15, were derived from the heat capacity data in the temperature range of 80 to 410 K with an interval of 5 K. The thermostability of the compound was further tested by DSC and TG measurements. The results were in agreement with those obtained by adiabatic calorimetry.     

Metal complexes of anxiolitic drugs. Crystal structure and electronic properties of dimeric oxalato complex of copper(II) bromazepam

Summary The title compound, has been prepared; its crystal structure, solved at room temperature, consists of dimer units bridged by oxalate lignads. Each copper ion is surrounded by two nitrogens of bromazepam and two oxygens of the oxalate ligand; a molecule of water occupies the apical site. The magnetic properties of the title compound have been investigated in the 30–300 K range. The molar magnetic susceptibility closely follows the behaviour expected for an antiferromagnetically coupled copper(II) binuclear complex with a singlet-triplet energy gap,J=–349 cm^–1.     

Molar heat capacities and standard molar enthalpy of formation of 2-amino-5-methylpyridine

The heat capacities (C _p,m) of 2-amino-5-methylpyridine (AMP) were measured by a precision automated adiabatic calorimeter over the temperature range from 80 to 398 K. A solid-liquid phase transition was found in the range from 336 to 351 K with the peak heat capacity at 350.426 K. The melting temperature (T _m), the molar enthalpy (Δ_fus H _m⁰), and the molar entropy (Δ_fus S _m⁰) of fusion were determined to be 350.431±0.018 K, 18.108 kJ mol⁻¹ and 51.676 J K⁻¹ mol⁻¹, respectively. The mole fraction purity of the sample used was determined to be 0.99734 through the Van’t Hoff equation. The thermodynamic functions (H _T-H _298.15 and S _T-S _298.15) were calculated. The molar energy of combustion and the standard molar enthalpy of combustion were determined, ΔU _c(C₆H₈N₂,cr)= −3500.15±1.51 kJ mol⁻¹ and Δ_c H _m⁰ (C₆H₈N₂,cr)= −3502.64±1.51 kJ mol⁻¹, by means of a precision oxygen-bomb combustion calorimeter at T=298.15 K. The standard molar enthalpy of formation of the crystalline compound was derived, Δ_r H _m⁰ (C₆H₈N₂,cr)= −1.74±0.57 kJ mol⁻¹.