Effect of bromine and substituted alkyl chain on the interfacial self-assembly of bromobenzene derivatives by scanning tunneling microscopy.

The self-assemblies of four compounds, 1-bromo-4-(hexadecyloxy)benzene (BHB-16), 1-bromo-4-(octadecyloxy)benzene (BOB-18), 1-bromo-4-(pentadecyloxy)benzene (BPB-15) and 1,4-dibromo-2,5-(dioctadecyloxy)benzene (DDB-18), have been studied on highly oriented pyrolytic graphite (HOPG) under ambient conditions by scanning tunneling microscopy (STM), with the aim of understanding the influence of the molecular structure and functional groups on the arrangements. It is found that the bromine atoms of the four molecules are in bright contrast and can be identified in STM images. The neighbouring phenyl head groups of the BHB-16, BOB-18 and BPB-15 molecules in one lamella, with an anti-parallel orientation, are interdigitated with different offset distance, while the aromatic cores of DDB-18 molecules in the same row are in a parallel orientation. Moreover, an odd-even effect is observed in the self-assemblies of the former three molecules as expected. The STM images of the four molecules resemble the calculated HOMO electron density contours somewhat with positive surface bias voltage. On the basis of comparative analysis between the STM images, it is suggested that the electrostatic attractions between the neighbouring molecules play an important role in the self-assemblies of BHB-16, BOB-18 and BPB-15, while it is the van der Waals force and the non-covalent halogen-halogen interaction that dominate the structure of DDB-18 adlayer.