The mixing properties of hexafluorobenzene with carbon tetrachloride and with perfluoromethylcyclohexane

Excess thermodynamic functions (free energies, enthalpies and entropies of mixing) have been obtained from measurements of vapour pressures, together with excess volumes of mixing, for mixtures of hexafluorobenzene with carbon tetrachloride and with perfluoromethyl-cyclohexane (tetradecafluoromethylcyclohexane). Deviations from thermodynamic ideality are large, although the systems are completely miscible. Critical temperatures of the mixtures are also reported. A correlation between the data, anticipated from a simple model for mixtures of asymmetric molecules, does not obtain.     

Density-functional theory study of electric and magnetic properties of hexafluorobenzene in the vapor phase

A series of electric and magnetic properties of hexafluorobenzene have been calculated, including the electric dipole polarizability, magnetizability, electric quadrupole moment, and nonlinear mixed electric dipole-magnetic dipole-electric quadrupole hyperpolarizabilities needed to obtain estimates of the Kerr, Cotton-Mouton, Buckingham, Jones, and magnetoelectric birefringences in the vapor phase. Time-dependent density-functional theory was employed for the calculation of linear-, quadratic, and cubic response functions. A number of density functionals have been considered, along with Sadlej's triple-zeta basis set and the augmented correlation-consistent polarized valence double zeta and augmented correlation-consistent polarized valence triple zeta basis sets. Comparisons have been made with experiment where possible. The analysis of results allows for an assessment of the capability of time-dependent density-functional theory for high-order electromagnetic properties of an electron-rich system such as hexafluorobenzene.     

Photoelectron spectroscopy of hydrated hexafluorobenzene anions

We present a synergetic experimental/theoretical study of hydrated hexafluorobenzene anions. Experimentally, we measured the anion photoelectron spectra of the anions, C6F6(-)(H2O)n (n=0-2). The spectra show broad peaks, which shift to successively higher electron binding energies with the addition of each water molecule to the hexafluorobenzene anion. Complementing these results, we also conducted density functional calculations which link adiabatic electron affinities to the optimized geometric structures of the negatively charged species and their neutral counterparts. Neutral hexafluorobenzene-water complexes are not thought to be hydrogen bonded. In the case of C6F6(-)(H2O)1, however, its water molecule was found to lie in the plane of the hexafluorobenzene anion, bound by two O-H...F ionic hydrogen bonds. Whereas in the case of C6F6(-)(H2O)2, both water molecules also lie in the plane of and are hydrogen bonded to the hexafluorobenzene anion but on opposite ends. This study and that of Schneider et al. [J. Chem. Phys. 127, 114311 (2007), preceding paper] are in agreement regarding the geometry of C6F6(-)(H2O)1.     

Reactions of hexafluorobenzene with some organometallic reagents

The inverse addition of trichloro-2-thienyl-lithium to hexafluorobenzene in THF or ether has given 1,4-bis(trichloro-2-thienyl) tetrafluorobenzene in addition to the tetrakis(trichloro-2-thienyl)difluorobenzene. n-Butyl-lithium with hexafluorobenzene gave mono, bis tris and tetrakis compounds whereas t-BuLi afforded only 1,4-bis(t-butyl)tetrafluorobenzene in excellent yield. Other organolithium and organomagnesium reagents gave the expected products. IR, ¹⁹F NMR and UV spectral data are presented for the several new compounds.     

Some perfluorocarbocyclic ethers and polyethers from hexafluorobenzene

High-resolution nuclear magnetic resonance (NMR) spectroscopy was used to determine the microstructures of some perfluorocarbocyclic ethers and polymers from reactions of bis(fluoroxy)-difluoromethane and hexafluorobenzene. The thermal and photochemical reactions of CF₂(OF)₂ and excess hexafluorobenzene are described. The structures of several new perfluoro-1,3-dioxolanes in which the rings constituted part of a bicyclic system were elucidated by ¹⁹F-NMR, gas chromatograph, gas chromatograph-infrared, and gas chromatograph-mass spectra. The copolymers of molecular weight about 2500 are, with 40% of the difluoromethylenedioxy groups, estimated by ¹⁹F-NMR to be in the polymer chain and the rest as pendant groups to the perfluorocyclohexylene and perfluorocyclohexenylene moieties. The suggested polymer structures are described and the mechanisms discussed.     

Physical properties of hexafluoroacetone

The vapour pressure of hexafluoroacetone has been determined from 58°C to the critical point. The critical temperature and pressure were also measured. Densities of the liquid and saturated vapour were determined between - 50°C and the critical point. Using this information the rectilinear diameter line and the heats of vaporization have been determined.     

Collisional deactivation of highly vibrationally excited hexafluorobenzene molecules

The collisional deactivation of the internal energy of vibrationally highly excited hexafluorobenzene (HFB) molecules was examined by the analysis of ultraviolet absorption spectra of excited HFB molecules produced by excitation with an ArF(193 nm) laser. The decay time profile of the internal energy was calculated from the observed absorption decay profile of the hot molecule using the conversion relation between the absorbance by hot molecules and the internal energy. Thus the average energy 〈ΔE〉 transferred per collision was estimated by two different models; energy-independent and energy-dependent function for the decay of the internal energy. The obtained values of 〈ΔE〉 indicate that the energy-dependent model may give reasonable values for 〈ΔE〉, but as far as the value of 〈ΔE〉 is concerned, the energy-independent model is likely to be applicable to the analysis in this reaction system. The collisional deactivation mechanism of the hot HFB molecule and the heating-up effect observed at shorter wavelengths are discussed on the basis of the conversion curve.     

Infrared spectrum of hexafluorobenzene crystal at 77 K

Infrared spectra of polycrystalline C₆F₆ are analyzed in the 200 cm⁻¹ to 4000 cm⁻¹ region. The vibrational frequencies agree well with liquid data although many of the bands are split. Mutual exclusion between infrared active and Raman active fundamentals is found.     

Effect of hexafluorobenzene on the photophysics of pyrene

Absorption and fluorescence spectroscopy studies reveal the formation of a weak complex between pyrene and C(6)F(6) even in very dilute systems. The complex affects the photophysics of pyrene and reveals a combination of static and dynamic-quenching phenomena in both polar and nonpolar solvents. The results are supported by computational studies that shed light on the structure of the complex and the interactions involved and suggest that ground and excited-state interactions are of comparable magnitude; the association is believed to be driven by quadrupolar interactions. Understanding these interactions in solution is important for applications that aim at controlling the regio- or stereoselectivity of organic reactions.     

Polymer films prepared from hexafluorobenzene in direct-current discharge

Polymer films with hydrophobic surface properties were prepared from hexafluorobenzene in a direct-current discharge. The films possess good dielectric characteristics (dielectric loss tangent and permittivity) in the temperature range 20–240°C. The composition and structure of this polymer were studied by means of IR spectroscopy and electron spectroscopy for chemical analysis with reference to mass-spectrometric data for the discharge gas phase.     

Reactions of HMPA with hexafluorobenzene, pentafluorochlorobenzene and pentafluorophenol

Hexamethylphophoramide (HMPA) reacted with hexafluorobenzene and its derivatives with good conversion to give dimethylaminated products and phosphorofluoridates, even in unfavorable reaction stoichiometries. An aromatic nucleophilic mechanism might be involved.