F···Br and F···S Heterohalogen-Bond-Directed 2D Self-Assemblies of a Benzothiadiazole Derivative.

Halogen bonding (XB) is of great importance in fabricating a two-dimensional (2D) self-assembly for its adaptive directionality. However, the XBs involving fluorine (F) have barely been studied due to the absence of an σ-hole on F. Here, 2D self-assemblies of a F-substituted 4,7-bis(5-bromo-4-dodecylthiophen-2-yl)-5,6-difluorobenzo[c][1,2,5]thiadiazole (BTZ-BrF) molecule on graphite were investigated using scanning tunneling microscopy (STM) and density functional theory (DFT) calculations. STM experiments revealed that the 2D patterns of BTZ-BrF had a clear solvent and concentration dependence, showing a frame-like pattern in aliphatic acid and aliphatic hydrocarbon solvents at high concentrations. At lower concentrations, a bamboo-like and a wave-like pattern were observed in aliphatic acid, whereas small frame-like and large ladder-like domains at high solution concentrations in aliphatic hydrocarbon were observed. As the concentration further decreased, two linear patterns were observed. DFT calculations suggested that the hetero-XBs of F···Br, F···S, Br···S, and Br···N, the homo-XBs of type-II Br···Br, and the S···S interactions synergistically directed and stabilized the polymorphic 2D architectures. This understanding of intermolecular XBs during the molecular assembly at the molecular level may shed light on the ongoing efforts of regulating nanostructures of multifunctional organics.