Influence of Different Substitution Patterns on the 2D Crystalline Aggregation of Small Molecules on HOPG Surfaces

A series of benzoic and terephthalic acid derivatives and their corresponding ethyl esters have been synthesized. These are decorated with dendritic units carrying alkoxy chains that differ in the number of alkoxy groups and/or their substitution pattern. These molecules were deposited from solution on highly oriented pyrolytic graphite, and the resulting supramolecular surface patterns have been studied by scanning tunneling microscopy at the solid/liquid interface. Thus, we were able to perform a systematic study on the influence of orthogonal functional groups governing the supramolecular assembly, that is, the alkoxy chains of dendritic units and the carboxylic acid (ester) functions, on the intermolecular interactions, that is, van der Waals interactions and hydrogen bonding between the adsorbed species that drive the pattern formation.