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The diverse self-assembly structures of macrocyclic molecule revealed with STM by adjusting the solution concentration.

Macrocyclic molecule [3]C 12 TT-TPA was synthesized by stille-coupling reaction though alternately connecting 4,7-bisthienyl-2,1,3-thienothiazole (B) unit and triphenylamine (A) unit. The concentration-dependent self-assembly structures of [3]C 12 TT-TPA were explored in liquid/solid interface by scanning tunneling microscopy and density functional theory. 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]C 12 TT-TPA molecules from liquid phase, which increases the molecule-molecule interactions and molecule-substrate interactions considerably. This study of fundamental exploration is important to understand the basic formation mechanisms and the stability of two-dimensional functional materials.