Synchrotron X-ray and neutron diffraction have been used to determine the two-dimensional crystalline structures of alkylamides adsorbed on graphite at submonolayer coverage. The calculated structures show that the plane of the carbon backbone of the amide molecules is parallel to the graphite substrate. The molecules form hydrogen-bonded dimers, and adjacent dimers form additional hydrogen bonds yielding extended chains. By presenting data from a number of members of the homologous series, we have identified that these chains pack in different arrangements depending on the number of carbons in the amide molecule. The amide monolayers are found to be very stable relative to other closely related alkyl species, a feature which is attributed to the extensive hydrogen bonding present in these systems. The characteristics of the hydrogen bonds have been determined and are found to be in close agreement with those present in the bulk materials.

Physisorbed monolayers based on relatively weak noncovalent interactions can serve as excellent model systems for understanding crystallization of materials in reduced dimensionality. Here we employ a powerful combination of scanning tunneling microscopy (STM), differential scanning calorimetry (DSC), and computational modeling to reveal two-dimensional (2D) crystallization and mixing behavior of saturated and unsaturated (cis as well as trans) aliphatic primary amides. The foundation of the present work is laid by DSC measurements, which reveal characteristic adsorption and mixing behavior of aliphatic amides. These results are further supported by STM visualization of the adlayers. STM reveals, at submolecular resolution, the adsorption as well as the two-component 2D phase behavior of these molecules at the liquid-solid interface. The saturated and trans-unsaturated amides exhibit random mixing in view of their size and shape complementarity. Binary mixtures of saturated and cis-unsaturated amides, on the other hand, display unprecedented mixing behavior. The linear saturated and bent cis-unsaturated amide molecules are found to mix surprisingly better at the liquid-solid interface than might have been expected on account of the dissimilarity in their shapes. Strong, directional intermolecular hydrogen-bonding interactions as well as the relative stabilization energies of the adlayers are responsible for such unusual mixing behavior. Computational modeling provides additional insight into all the possible interactions in 2D assemblies and their impact on stabilization energies of the supramolecular networks. This study provides a model for understanding the effect of nanoscale cocrystallization on the thin film structure at interfaces and demonstrates the importance of molecular geometry and hydrogen bonding in determining the coadsorption behavior.

In this work we present a study on the adsorption of linear alkyl aldehydes physisorbed from their bulk liquid onto a graphite substrate combining calorimetry for all homologues from C6 to C13, with more detailed diffraction, incoherent neutron scattering, and scanning tunneling microscopy techniques for one (C12) representative member. We identify solid monolayer formation for some of these species for alkyl chain lengths of 6 to 13 carbons at high surface coverages. The C12 monolayer structure is determined to be most likely Pgg and this structure is discussed in terms of the importance of dipolar interactions.

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