The STM results of the air-exposed BOPHY/Ag(111) sample show a transformation in the oligomers from linear structures into kinked ones, with a periodicity of around 1.1 nm (Figure ), which again could indicate the formation of covalent BOPHY-based oligomers. To better understand this process, we have performed DFT-based calculations on different possible scenarios considering the XPS results and some of the most abundant oxygen-containing species present in air (Figure ). The initial case where the BOPHY molecules are coordinated to Ag atoms presents an energy stored at the C-Ag bonds of -1.64 eV. If we consider the displacement of the Ag atom by a CO molecule, the resulting structure would present an energy gain of 0.84 eV (C-CO bond energy of -2.48 eV). On the other hand, if the Ag atom were replaced by an oxygen atom, the bond energy would increase to -3.20 eV, making it the most stable situation. Thus, our DFT results suggest the unexpected formation of ether-bridged covalent oligomers upon exposure to air. It must be noted that the incorporation of this extra atom in between BOPHY molecules separates the molecules enough so that they do not feel the steric repulsion between the methyl groups, allowing for the covalent bonding between them.