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In this work,two aza-BODIPY derivatives,3,5-diphenyl-1,7-di(p-dodecyloxyphenyl)-aza-BODIPY (CJF)and 3,5-di(p-bromophenyl-1,7-di(p-dodecyloxyphenyl)-aza-BODIPY (2Br-CJF) acted as model molecules to form the self-assembly monolayers on the solid-liquid interface.With the utilizing of scanning tunnelling microscope (STM),we demonstrated that intermolecular Br…F-BF interactions existed in 2Br-CJF self-assembly structure and played an important role in strengthening the stability of 2Br-CJF self-assembly structure.This result is supported by density functional theory (DFT) calculation.