Identifying Target Molecule and Trace Amount of the Byproduct by Two-Dimensional Self-Assembly with Different Solution Concentrations.

Scanning tunneling microscopy (STM) is a powerful way to realize the recognition of self-assembled nanostructures on the atomic scale. In this article, dihexadecyl 6,9-bis((4-(hexadecyloxy)phenyl)ethynyl) phenanthro[9,10- c ]thiophene-1,3-dicarboxylate (D-PT) and dihexadecyl 6-bromo-9-((4-(hexadecyloxy) phenyl)ethynyl)phenanthrol[9,10- c ]thiophene-1,3-dicarboxylate (S-BrPT) with different substituents were chosen as the target system. D-PT with four side chains as the target molecule and S-BrPT with three side chains and a bromine substituent as the byproduct were mixed in a molar concentration ratio of 20:1. The effect of solution concentration on the molecular self-assembly of the mixture was investigated by STM at the hexadecane/HOPG interface. At high concentrations, only D-PT molecules formed a dimer pattern resulting from the intermolecular van der Waals force and self-adaption. Further diluting the solution, D-PT formed the coexisting dimer and linear structures, in which the linear pattern was formed via solvent coadsorption. At low concentrations, S-BrPT molecules forming N-shaped dimers appeared and filled the linear structure fabricated by D-PT molecules. With further decrease in the concentration, S-BrPT molecules formed N-shaped dimers covering almost half of the surface area, resulting from the C-Br···π and Br···H-C bonds. At very low concentrations, S-BrPT molecules formed N-shaped dimers to arrange the matrix architecture due to the coadsorption of more hexadecane molecules. Density functional theory (DFT) calculations demonstrated that the stronger intermolecular C-Br···π and Br···H-C bonds were significant factors in determining the formation of N-shaped dimers and the stability of this nanostructure. This work enriches the diversity of self-assembled motifs and provides a strategy to characterize different symmetric molecules with trace amounts in a mixed system by STM.