Abstract
A direct calorimetric measurement of the overall enthalpy change associated with self-assembly of organic monolayers at the liquid-solid interface is for most systems of interest practically impossible. In previous work we proposed an adapted Born-Haber cycle for an indirect assessment of the overall enthalpy change by using terephthalic acid monolayers at the nonanoic acid-graphite interface as a model system. To this end, the sublimation enthalpy, dissolution enthalpy, the monolayer binding enthalpy in vacuum, and a dewetting enthalpy are combined to yield the total enthalpy change. In the present study the Born-Haber cycle is applied to 4,4'-stilbenedicarboxylic acid monolayers. A detailed comparison of these two aromatic dicarboxylic acids is used to evaluate and quantify the contribution of the organic backbone for stabilization of the monolayer at the nonanoic acid-graphite interface.
Highlights
Supramolecular self-assembly is an ubiquitous approach for the bottom-up fabrication of functional nanostructures
In previous work we proposed an adapted Born–Haber cycle for an indirect assessment of the overall enthalpy change by using terephthalic acid monolayers at the nonanoic acid–graphite interface as a model system
In the present study we utilize the method proposed in ref. 4 to evaluate the thermodynamics of 4,40-stilbenedicarboxylic acid (SDA) monolayer self-assembly at the nonanoic acid–graphite interface
Summary
Supramolecular self-assembly is an ubiquitous approach for the bottom-up fabrication of functional nanostructures. By using established concepts for the concentration dependence of the chemical potential, e.g. ideal or regular solutions, the free energy of competing monolayer structures can be evaluated and compared. This approach was successfully employed to explain the concentration dependent transition from a densely packed to a porous polymorph[20] or the emergence of different bimolecular phases.[14] Recently De Feyter et al extended this approach by using the concentration dependence of the transition temperature of a structural
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