It was found that in phenylbenzenes and phenylnaphthalenes the cohesive energy of the crystal phase increases as more molecular surface area becomes available for establishing intermolecular interactions. Several 1-arylnaphthalenes and 1,8-diarylnaphthalenes were synthesized by the Suzuki-Miyaura reaction, showing significant differentiation in the yields and selectivity between aryl rings with electron donating (higher yields/selectivity), and electron withdrawing substituents (lower yields/selectivity). The global results obtained were grouped into relevant subjects, and thoroughly analyzed in order to explore the following fields: the Suzuki-Miyaura reaction mechanism the structural/energetic relationships in some azabenzenes, polyphenylbenzenes, phenylnaphthalenes, and benzyl ketone derivatives aromatic interactions.
Whenever possible, the experimental results were complemented with computational chemistry at the B3LYP and MP2 levels of theory. Dynamic 1H NMR spectroscopy was performed on some relevant systems in order to explore molecular dynamics. Through combination of the combustion and sublimation results, the standard molar enthalpies of formation in the gas phase, at T = 298.15 K, were derived and used to infer about gas phase energetics. For some compounds, Calvet microcalorimetry was used for the determination of standard molar enthalpies of sublimation, at T = 298.15 K.
The Knudsen/Quartz crystal effusion technique was employed for the measurement of vapour pressures as a function of temperature, and derivation of standard molar enthalpies, entropies and Gibbs energies of sublimation, at T = 298.15 K. Static mini-bomb and macro-bomb combustion calorimetry was employed for the determination of standard molar enthalpies of formation in the crystalline phase, at T = 298.15.
The great majority of the compounds under study was synthesized by the Suzuki-Miyaura cross-coupling reaction, and characterized by 1H and 13C NMR spectroscopy and by X-ray crystallography.
In this work, a series of organic aromatic compounds was studied by various experimental and theoretical methods, with the main objective of obtaining insights about the physical-chemical factors that might lead to structural and energetic differentiation among selected groups of interrelated molecules.
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