Analysis of the magnetic coupling in nitroxide organic biradicals

The magnetic coupling in organic biradicals has been analyzed by means of ab initio wave function-based methods. Attention is focused on the coupling between the spin moments localized on the NO-groups in meta and para phenylene-bridged nitroxides, and bis(nitronyl) nitroxide and bis(imino) nitroxide biradicals. The leading mechanisms governing the coupling have been isolated by means of class-partitioned CI calculations. It was found that the mechanisms of the coupling in the para and meta phenylene-bridged nitroxides are similar to that found in transition metal complexes, while for the other biradicals the dominance of other mechanisms (like the spin polarization) imposes restrictions on the computational strategy to be followed to best estimate the coupling.     

Toward an effective yet reliable many-body computation of magnetic couplings in bisnitronyl nitroxide biradicals

Configuration interaction calculations have been applied to the study of the magnetic coupling in a series of bisnitronyl nitroxide diradicals. Molecular orbitals obtained with different localization schemes have been considered in the generation of the configuration interaction space, with the aim of investigating the role played by the various fragments in the magnetic interaction. Polyene spacers are found significant, while fragments outside the magnetic-bridge-magnetic moiety can be neglected.     

1H and 13C endor on phenoxyl biradicals randomly oriented in frozen solution

ENDOR measurements have been performed on ¹³C labelled biradicals, namely Yang's biradical and p-phenylenebisgalvinoxyl, in frozen solutions. Besides intense ENDOR lines at the free nuclear Zeeman frequencies, hyperfine shifted ¹H and ¹³ ENDOR lines could be detected with excellent signal-to-noise ratios. From these spectra not only the magnitudes, but also the signs of the hyperfine splitting components relative to the zero field splitting parameter D could be derived. It is demonstrated that the sign of D in Yang's biradical must be negative. This may be due to a spin-orbit coupling contribution to the zero field splitting parameter.     

Compressibilities of cyclohexane and toluene mixtures at various temperatures

The isothermal compressibilities _T for cyclohexane+toluene mixtures at 25, 35, 45 and 60°C have been determined by direct piezometric measurement. By combining our results with supplementary literature data, we have calculated the isentropic compressibility _S. Values of the excess functions (V^E/_p)_T, _T ^E and _S ^E were also calculated at four temperatures and their behavior as a function of mole fraction and temperature was studied.     

Immersion enthalpy of benzene/cyclohexane and toluene/cyclohexane binary mixtures into modified activated carbons

Journal of Thermal Analysis and Calorimetry - The interaction between binary mixtures of benzene/cyclohexane and toluene/cyclohexane into three activated carbons with different physical and...     

Study on the heteroatom influence in pyridine-based nitronyl nitroxide biradicals with phenylethynyl spacers on the molecular ground state

Novel pyridine-based nitronyl nitroxide (NIT) biradicals, 3,5-bis[4-(1-oxyl-3-oxo-4,4,5,5-tetramethylimidazolin-2-yl)phenylethynyl)]pyridine (1) and 2,6-bis[4-(1-oxyl-3-oxo-4,4,5,5-tetramethylimidazolin-2-yl)phenylethynyl)]pyridine (2), and monoradicals, 4-(5-bromopyridine-3-ylethynyl)-1-(1-oxyl-3-oxo-4,4,5,5-tetramethylimidazolin-2-yl)benzene (3), 4-trimethylsilylethynyl-1-(1-oxyl-3-oxo-4,4,5,5-tetramethylimidazolin-2-yl)benzene (4), and 4-trimethylsilylethynyl-1-(1-oxyl-3-oxo-4,4,5,5-tetramethylimidazolin-2-yl)pyridine (5), were synthesized and investigated by ESR and UV-vis spectroscopy. The solution EPR measurements of the biradicals gave well-resolved, nine-line spectra with exact half line spacing as compared to monoradicals (giso = 2.0067) with isotropic line spacing /aN/= 7.36 G. This indicates strong, intramolecular exchange coupling (J > 7 x 10(-4) cm(-1); J/aN > 1) of the biradicals with in the limit of EPR. The temperature dependence on the Deltams = +/-2 signal intensity of biradicals follow Curie behavior down to 4 K ascertaining the triplet ground state or its near-degeneracy with the singlet state. UV-vis studies of 1-5 show characteristic differences in the extinctions of n-pi transitions around 600 nm. Both biradicals 1 and 2 were crystallized in monoclinic space groups C2/c and P2(1)/a with the intraradical distances 1.54 and 1.47 nm, respectively. Computational studies of the biradicals 1, 2, and 1,3-bis[4-(1-oxyl-3-oxo-4,4,5,5-tetramethylimidazolin-2-yl)phenylethynyl)]benzene (T) were performed by the AM1/CAS(8,8) method to calculate the singlet-triplet (DeltaEST) energy difference and the spin density distribution. Results show that the position of the pyridyl nitrogen in 1 and 2 in comparison with T does not alter the triplet ground-state spin multiplicities supporting the obtained experimental results.     

The adsorption of polyoxyethylated nonylphenol in cyclohexane solution

Summary The adsorption of polyoxyethylated nonylphenol on calcium carbonate and on carbon black in cyclohexane was studied and compared with that in water. The adsorption of this nonionic surfactant in cyclohexane on calcium carbonate showed a monolayer adsorption isotherm and that on carbon black showed a multilayer adsorption isotherm. The adsorption cross sectional area,A, of the surfactant molecule increased with the number of the ethylene oxide units,n, in both cases, and expressed by the equationsA=49.1n ^0.34 for the former case andA=270.n ^0.29 for the later case.When either one of the adsorbent or the solvent is polar and the other is nonpolar, the adsorbed molecules form simple oriented monolayer. When both of the adsorbent and the solvent are polar or nonpolar, however, the adsorption takes place in a complicated form and is delicately affected by the impurity and the balance of the polarity of the surfactant molecule.

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Zusammenfassung Die Adsorption von Polyoxyäthylen-nonylphenol an Calciumcarbonat und Ruß in Zyklohexan wurde untersucht und das Adsorptionsverhalten mit den Ergebnissen von wäßrigen Lösungen verglichen, die im letzten Bericht mitgeteilt sind. Die Adsorption dieser nichtionischen oberflächenaktiven Substanz in Zyklohexan an Calciumcarbonat zeigte eine monomolekulare und an Ruß eine höhermolekulare Adsorptionsisotherme. In beiden Fällen nahm der Adsorptionsquerschnitt,A, des oberflächenaktiven Moleküls mit der Anzahl der Äthylenoxid-Einheiten,n, zu, und es galten folgende Werte:A=49.1 n^0.29 im ersten Fall undA=270.n ^0.34 im letzten Fall.Die adsorbierten Moleküle bilden eine einfach orientierte monomolekulare Schicht, wenn von den beiden Komponenten Adsorbens oder Lösungsmittel eines polar und das andere unpolar ist. Wenn jedoch beide polar oder nichtpolar sind, verläuft die Adsorption komplizierter und wird von den Verunreinigungen und der Bilanz der Polarität empfindlich beeinflußt.

     

Temperature and phase dependence of positron lifetimes in solid cyclohexane

The temperature dependence of position lifetimes in both the brittle and plastic phases of cyclohaxane has been examined. Long-lived components in both phases are associated with the formation of positronium (Ps). Two long lifetimes attributable to ortho-Ps are resolvable in the plastic phase. The longer of these (≈ 2.5 ns), which is temperature dependent, is ascribed to ortho-Ps trapped at vacancies. The shorter lifetime (≈ 0.9 ns), shows little temperature dependence. In contrast to most other plastic crystals, no sigmoidal behaviour of the average ortho-Ps lifetime is observed. A possibility exists that some self-trapping of Ps may occur just above the phase transition. In the brittle phase only one long lifetime of ≈ 1.1 ns is resolvable. The presence of 100 ppm impurities reduces the ortho-Ps yield, especially in the brittle phase, but does not influence the lifetimes. The ratio between the apparent ortho-Ps and para-Ps, yields is close to 3 for the pure-crystals in the plastic phase, but smaller in the brittle phase. A correlation is established between the molecular packing coefficients for plastic and brittle crystals and the ortho-Ps lifetime in the crystals.     

Reaction of toluene with ozone in the liquid phase

Reaction of toluene with ozone in acetic anhydride was studied. The dependence of the direction, selectivity, and extent of oxidation on the reaction temperature, solvent nature, and catalyst composition was examined.     

Acoustic absorption and dynamic compressibility studies of dilute and concentrated solutions of polystyrene in toluene and cyclohexane

Acoustic absorption and adiabatic compressibility measurements are reported on solutions of polystyrene (M_n = 89,000) in toluene and cyclohexane. The data in toluene cover a temperature range from 293 to 343°K and a concentration range of 10–400 Kg m^?3 (1–40 wt%). The dependence of acoustic absorption on concentration was found to be linear up to 100 kg m^?3, which corresponds to the concentration at which polymer–polymer interactions cause significant changes in the specific viscosity-concentration relationship. Up to 200 kg m^?3 the data could be fitted to computations based on an artificial separation of the dispersion into contributions from viscoelastic and segmental processes, using parameters obtained from a study of narrow molecular weight distribution samples at 25 kg m^?3. However, neither approach was capable of describing dispersions in the 300, 400 kg m^?3 solutions. The modification of the relaxation spectrum observed at the highest concentrations is ascribed to volume and entropy changes associated with alterations of the local environment around a segment of the polymer chain. These changes have their origin in interchain penetration and polymer–polymer contacts, and indicate that ‘entanglement’ is primarily entropic in effect. The adiabatic compressibility exhibited similar deviations from a simple concentration dependence, and allowed estimation of an incompressible volume increment associated with polymer–polymer interactions in the high-concentration entangled matrix. However, the adiabatic compressibilities of solutions of polystyrene, 10–15 kg m^?3, in cyclohexane showed no deviations from simple behavior in the region of the theta temperature. Measurements of the adiabatic compressibility of polystyrene in mixtures of cyclohexane-toluene have been used to obtain the relative magnitude of solvent and polymer contributions to the excess compressibility.     

The rotational mobility of fulleropyrrolineoxyl in toluene solution

The rotational mobility of a stable fullerene-based nitroxyl radical (fulleropyrrolineoxyl) in toluene was studied. The rotational correlation time of fulleropyrrolineoxyl was found to be about eight times longer than that of 4-oxy-2,2,6,6-tetramethylpiperidine-1-oxyl. The activation energy of the rotational motion of both probes was determined and their hydrodynamic radii estimated.     

Stability of Complex Metal Bromides in the gas phase and in toluene

The equilibrium constants of the reactions MBr₂(s) + Al₂Br₆(sln) ? MAl₂Br₈(sln) M = Cr, Mn, Co, Ni, Zn, Cd have been measured at 298 K in toluene. Ni: 0.017 ± 0.0024, Co: 0.54 ± 0.07, Zn: 1.5 ± 0.2, Mn: 2.1 ± 0, 7, Cr: 2.2 ± 1, Cd: 7 ± 5. They are compared with literature values of the equilibrium constants of analogous reactions in the gas phase MX₂(s) + Al₂X₆(g) ? MAl₂X₈(g), X = Cl, Br. For CoAl₂Br₈(sln) the temperature dependence of the equilibrium constant yielded Δ_fH = ?9.4 ± 1 kJ mol^?1 and Δ_fS = ?39.5 ± 3 J mol^?1 K^?1 while literature values for CoAl₂Br₈(g) are Δ_fH = 42.4 ± 2 kJ mol^?1 and Δ_fS = 42.9 ± 2 J mol^?1 K^?1. The solubility of Al₂Br₆ in toluene as well as its enthalpy of dissolution have been measured in order to evaluate ΔH° and ΔS° of the solvation of Al₂Br₆(g) and CoAl₂Br₈(g) in toluene by a thermodynamic cycle. Solvation of Al₂Br₆(g): ΔH = ?72.7 ± 1 kJ mol^?1, ΔS = ?139.6 ± 4 J mol^?1 K^?1, solvation of CoAl₂Br₈(g): ΔH = ?124.5 ± 4kJ mol^?1, ΔS = ?222 ± 9J mol^?1 K^?1. Thus, CoAl₂Br₈ interacts more strongly with the solvent toluene than Al₂Br₆ does.     

Cloud-point curves for polystyrenes of low polydispersity in cyclohexane solution

Cloud-point curves and relative volumes of the coexisting phases just below the cloud-point temperatures were observed for a commercial sample of “monodisperse” polystyrene and one of its fractions. As expected from theoretical considerations, the cloud-point curve for the more monodisperse sample was flatter near the peak over a greater concentration range than that of the parent sample. Furthermore, the critical point for the fraction appeared to be closer to the peak of the cloud-point curve than was that of the unfractionated polymer. In addition, it was learned that one type of impurity could be detected with extraordinary sensitivity by means of the cloud-point curve.