Phenylnaphthalenes: sublimation equilibrium, conjugation, and aromatic interactions.

Centro de Investigação em Química, Departamento de Química e Bioquímica, Faculdade de Ciências da Universidade do Porto, P-4169-007 Porto, Portugal.
The Journal of Physical Chemistry B (Impact Factor: 3.38). 02/2012; 116(11):3557-70. DOI: 10.1021/jp2111378
Source: PubMed

ABSTRACT In this work, the interplay between structure and energetics in some representative phenylnaphthalenes is discussed from an experimental and theoretical perspective. For the compounds studied, the standard molar enthalpies, entropies and Gibbs energies of sublimation, at T = 298.15 K, were determined by the measurement of the vapor pressures as a function of T, using a Knudsen/quartz crystal effusion apparatus. The standard molar enthalpies of formation in the crystalline state were determined by static bomb combustion calorimetry. From these results, the standard molar enthalpies of formation in the gaseous phase were derived and, altogether with computational chemistry at the B3LYP/6-311++G(d,p) and MP2/cc-pVDZ levels of theory, used to deduce the relative molecular stabilities in various phenylnaphthalenes. X-ray crystallographic structures were obtained for some selected compounds in order to provide structural insights, and relate them to energetics. The thermodynamic quantities for sublimation suggest that molecular symmetry and torsional freedom are major factors affecting entropic differentiation in these molecules, and that cohesive forces are significantly influenced by molecular surface area. The global results obtained support the lack of significant conjugation between aromatic moieties in the α position of naphthalene but indicate the existence of significant electron delocalization when the aromatic groups are in the β position. Evidence for the existence of a quasi T-shaped intramolecular aromatic interaction between the two outer phenyl rings in 1,8-di([1,1'-biphenyl]-4-yl)naphthalene was found, and the enthalpy of this interaction quantified on pure experimental grounds as -(11.9 ± 4.8) kJ·mol(-1), in excellent agreement with the literature CCSD(T) theoretical results for the benzene dimer.

  • [Show abstract] [Hide abstract]
    ABSTRACT: The standard (p o = 0.1 MPa) molar enthalpies of formation, in the gaseous phase, of 2-, 3- and 4-bromobenzonitrile isomers were calculated from the combination of the following two parameters experimentally determined: the standard molar enthalpy of formation in the condensed phase, derived from the standard molar energy of combustion in oxygen at T = 298.15 K, measured by rotating-bomb combustion calorimetry, and the standard molar enthalpy of sublimation at the same reference temperature, derived from vapour pressure studies at several temperatures, as measured by mass-loss Knudsen effusion. The computational calculations complement the energetic study and analysis of the electron delocalization allows a comparison between the fluorine and bromine benzonitrile isomers. The harmonic oscillator model of aromaticity and nucleus-independent chemical shift aromaticity criteria and the natural bond orbital analysis were applied and related with the intramolecular enthalpic interactions. The intermolecular interactions in the crystal packing were analysed in terms of enthalpic and entropic contributions, using the crystallographic structures available in literature.
    Structural Chemistry 12/2013; 24(6). DOI:10.1007/s11224-013-0278-1 · 1.90 Impact Factor
  • [Show abstract] [Hide abstract]
    ABSTRACT: In this work a new solution-based calorimetry approach for determination of the sublimation and vaporization enthalpies of low volatile compounds was proposed. The approach is based on the measurement of solution enthalpy of a molecule of interest in benzene and as well as the measurement of molar refraction index for this molecule. Enthalpies of solution at infinite dilution in benzene for a set of 18 aromatic and polyaromatic hydrocarbons were measured at 298.15 K. Experimental data on vaporization/sublimation enthalpies for this set were collected from the literature. For validation of the literature data additional sublimation experiments were performed for phenanthrene, 1-phenylnaphthalene, 1,2-diphenylbenzene, 1,2,3,4-tetraphenylnaphthalene, hexaphenylbenzene, and rubrene using transpiration, quartz crystal microbalance, and thermogravimetry. Vaporization/sublimation enthalpies derived from the solution calorimetry approach were in good agreement (within experimental uncertainties) with those measured by conventional methods. The solution-based calorimetry approach gives a reliable and quick appraisal of vaporization/sublimation enthalpies. This approach constitutes a complementary additional thermochemical option for vaporization/sublimation enthalpies data evaluation as well as for rapid data gathering for low volatile and/or thermally unstable organic compounds.
    Thermochimica Acta 08/2014; 589:164–173. DOI:10.1016/j.tca.2014.05.033 · 2.11 Impact Factor
  • [Show abstract] [Hide abstract]
    ABSTRACT: A structural study of three synthesized stereoisomeric oximes, (−)-8-phenylmenthyl glyoxylate oxime (8-PMGO), (+)-8-phenylneomenthyl glyoxylate oxime (8-PnMGO), and (−)-8-phenylisoneomenthyl glyoxylate oxime (8-PinMGO), was performed by means of variable temperature 1H NMR spectroscopy, X-ray crystallography, and ab initio calculations. It was found that in 8-PMGO a conformation where the phenyl and oxime moieties are stacked is significantly favored, whereas in the other stereoisomers this preference was not so evident. The conformational differences found between the isomers were used to rationalize the outcome of the reaction (simultaneous 1,3-cycloaddition and aza-Diels–Alder reaction) between the referred oximes and cyclopentadiene, in which the stereoselectivity was evaluated and found to be nicely reproduced by a simple conformational analysis. The global results indicate that the stereoselectivity of the studied oximes, a bit higher for 8-PMGO, originates from their particular conformational distribution, in which the phenyl∙oxime aromatic interaction plays a decisive role.
    Tetrahedron 06/2013; 69(24):5048-5057. DOI:10.1016/j.tet.2013.03.033 · 2.82 Impact Factor


Available from
Jun 1, 2014