We investigated the self-assembly of trimesic acid (TMA) at the solution–graphite interface by using scanning tunneling microscopy (STM). We show that the polymorphism of the adsorbate structures of TMA can be controlled by the substrate temperature during the deposition of the molecules out of the solution for various solvents of different polarity. TMA was dissolved in phenyloctane, octanoic acid, and undecanol. At elevated substrate temperatures, various periodic assemblies of TMA could be obtained. By increasing the temperature of the preheated substrate, the specific 2D supramolecular network structure and the corresponding packing density can be precisely tuned in each kind of the solvents studied. The results found by STM are explained by the increased concentration of the solution at the preheated substrate as well as the higher mobility of the solute molecules increasing the opportunity of interactions between the molecules, in particular different hydrogen bonding motifs. Our interpretation is supported by simulations for each structure using the semiempirical quantum-chemical method PM6-DH+.

No abstract

Benzene-1,3,5-triphosphonic acid (BTP) contains three non-planar phosphonic acid groups which enable three-dimensional hydrogen bonding. Because of these versatile 3D functional groups, BTP is an interesting intermediate to design both 2D and 3D supramolecular hydrogen-bonded architectures and organic-inorganic hybrid frameworks. However, the adsorption of BTP has surprisingly not been the subject of scanning tunneling microscopy (STM) investigations so far. Here a STM study of the adsorption pattern of BTP as obtained from deposition out of a solution in undecanol on an interface to highly-oriented pyrolytic graphite (HOPG) is presented. Furthermore, the influence of the substrate temperature during the deposition from solution on the self-assembly is investigated. High-resolution STM images reveal that the BTB molecules usually form various structures by co-adsorption with undecanol and that the BTP molecules as parts of self-assembled aggregates adsorb with their benzene ring planes tilted with respect to the substrate plane. The specific supramolecular pattern and the 2D packing density of BTP can be precisely tuned by adjusting the initial substrate temperature during deposition. The experimental results are compared to corresponding model structures obtained from semi-empirical simulations and explained by the influence of temperature on the concentration at the solution-solid interface and the kinetics of the self-assembly process. Based on these results, the control of the deposition substrate temperature has been proven to be a versatile tool to control the polymorphism of molecular patterns deposited out of solutions.