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Phase equilibria in the C60 + ferrocene system and solid-state studies of the C60·2ferrocene solvate

par Espeau, Philippe;Barrio, María;López, David Orencio;Tamarit, Josep Ll I J.L.;Céolin, René;Allouchi, Hassan;Agafonov, Viatcheslav;Masin, Francis ;Szwarc, Henri
Référence Chemistry of materials, 14, 1, page (321-326)
Publication Publié, 2002

Article révisé par les pairs

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Résumé :

Triclinic C60·2ferrocene, which melts peritectically at 495 K (ΔπH = +50 J g-1), can form by direct union of its components with a negative excess volume of -68Å3 per formula unit, although the enthalpy of deferrocenation into fcc C60 and ferrocene vapor is virtually the same as for the sublimation of pure ferrocene. C60 solubility in molten ferrocene is about 0.5 mol % at 495 K. The strong anisotropy of the thermal expansion tensor illustrates the anisotropy of intermolecular interactions inferred from the crystal structure in the 90-300 K range. The existence of nonnegligible interactions is corroborated by the persistence of the crystalline local order in the amorphous phase obtained by grinding, which reverts to the initial crystalline phase upon heating. Thus, from the thermodynamic and structural points of view, C60·2ferrocene behaves as the C60·2S8 solvate.