Tuning the Packing Density of 2D Supramolecular Self-Assemblies at the Solid−Liquid Interface Using Variable Temperature

The two-dimensional (2D) crystal engineering of molecular architectures on surfaces requires controlling various parameters related respectively to the substrate, the chemical structure of the molecules, and the environmental conditions. We investigate here the influence of temperature on the self-assembly of hexakis(n-dodecyl)-peri-hexabenzocoronene (HBC-C12) adsorbed on gold using scanning tunneling microscopy (STM) at the liquid/solid interface. We show that the packing density of 2D self-assembled HBC-C12 can be precisely tuned by adjusting the substrate temperature. Increasing the temperature progressively over the 20−50 °C range induces three irreversible phase transitions and a 3-fold increase of the packing density from 0.111 to 0.356 molecule/nm2. High-resolution STM images reveal that this 2D packing density increase arises from the stepwise desorption of the n-dodecyl chains from the gold surface. Such temperature-controlled irreversible phase transitions are thus a versatile tool that can then be used to adjust the packing density of highly ordered functional materials in view of applications in organic electronic devices.