Figure shows a STM image of the Au(111) surface after evaporation of I-BOPHY-I molecules at RT. As it can be observed, the molecular deposition leads to the formation of linear molecular rows that coexist with regions of apparently disordered molecular features (see black and green arrows, respectively). For the linear molecular arrangement, different domains, rotated by 120°, can be observed (compare regions of blue and black arrows), indicating a preferential molecular orientation associated to the characteristic three-fold symmetry of the substrate. A zoom of the STM image (Figure ) allow us to distinguish that these molecular rows are composed of double bright lobes. Two different characteristic lengths can be defined: 0.8 nm, corresponding to the separation between bright lobes within the rows, and 1.2 nm, between lobes of neighboring rows (red and black double arrows, respectively). Despite one could a priori be tempted to assign the lobes within rows to the molecular units, a careful analysis indicates the opposite. On the one hand, this separation (0.8 nm) is too small to accommodate a I-BOPHY-I molecule (1.3 nm) unless it is considered that the bright lobes correspond to some internal molecular feature. On the other hand, when Figure is analyzed in detail, it can be noticed that the edges of the ordered islands are composed by single lobe chains (see, for example, last row to the right of blue arrow). Thus, molecular units are assigned to lobes from neighboring rows. To corroborate our model, DFT theoretical calculations on the self-assembly of I-BOPHY-I molecules have been carried out. Figure shows the result of such calculations, which unambiguously reinforce the validity of our model and indicate that the bright lobes correspond to the iodine atoms attached to the molecules. At this point, it is interesting to note that, within the ordered phase, it is possible to distinguish two different assemblies (see Figure ): homogeneous rows and bunched double rows (black and yellow arrows in Figure , respectively). It should be noted that the I-BOPHY-I is a prochiral molecule, thus, when deposited on the surface, it will express its chirality depending on the face in contact with the underlying metallic surface (see (RR or SS) I-BOPHY-I schematic representations in Figure ). Taking this into account, we attribute this different assembly to the chiral organization of the molecules. In the former case, the rows are homochiral, allowing for a denser packing due to the establishment of halogen bonds between the F atoms of neighboring molecules (see model in Figure ), while in the bunched case, a heterochiral arrangement stabilized by intermolecular F-H bonds occurs (Figure ). However, as it will be shown below, this prochirality will not play any role on the formation of the hybrid oligomers.