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Enthalpy–Entropy Compensation Combined with Cohesive Free‐Energy Densities for Tuning the Melting Temperatures of Cyanobiphenyl Derivatives
Author(s) -
Dutronc Thibault,
Terazzi Emmanuel,
Guénée Laure,
Buchwalder KerryLee,
Spoerri Aurore,
Emery Daniel,
Mareda Jiri,
Floquet Sébastien,
Piguet Claude
Publication year - 2013
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201300587
Subject(s) - thermodynamics , enthalpy , intermolecular force , entropy of fusion , materials science , entropy (arrow of time) , melting temperature , melting point depression , chemistry , molecule , enthalpy of fusion , differential scanning calorimetry , physics , organic chemistry , composite material
This work illustrates how minor structural perturbations produced by methylation of 4′‐(dodecyloxy)‐4‐cyanobiphenyl leads to enthalpy–entropy compensation for their melting processes, a trend which can be analyzed within the frame of a simple intermolecular cohesive model. The transformation of the melting thermodynamic parameters collected at variable temperatures into cohesive free‐energy densities expressed at a common reference temperature results in a novel linear correlation, from which melting temperatures can be simply predicted from molecular volumes.