Diverse Self-assembly Structures of a Macrocycle Revealed with STM by Adjusting the Solution Concentration

The macrocyclic molecule [3]C₁₂ TT-TPA was synthesized by a Stille coupling reaction through alternately connecting 4,7-bisthienyl-2,1,3-thienothiazole and triphenylamine units. The concentration-dependent self-assembly structures of [3]C₁₂ TT-TPA were explored in liquid/solid interface by scanning tunneling microscopy and density functional theory. After increasing the solution concentration, five different nanostructures were constructed and the molecular packing densities were gradually enhanced. Those structural transformations from loose structures to compact structures are thermodynamically favourable because those transformations are accompanied by the adsorption of more [3]C₁₂ TT-TPA molecules from liquid phase, which increases the interactions between molecules and the interactions between molecules and substrate considerably. This study of fundamental exploration is important to understand the basic formation mechanisms and the stability of two-dimensional functional materials.