Influence of the substrate in the on-surface synthesis and air stability of 1D metal-organic oligomers

• Metal-organic BOPHY-based oligomers are synthetized on Au(1 1 1) and Ag(1 1 1) using the native metal adatoms. • The length and the synthesis temperature are determined by the reactivity of the metallic surface. • The stability of the oligomers on Au(1 1 1) is higher than on Ag(1 1 1) upon air exposure. • Metal-organic oligomers on Ag(1 1 1) transform into ether-bridged ones when exposed to air. The development of applicable functional materials currently stands as one of the main challenges in the field of on-surface synthesis. In this direction, it is necessary to understand their stability in real conditions, what it is known as bridging the pressure gap . Interestingly, although it is well-established that the on-surface synthesis will be highly influenced by the selected substrate, little is known about the effect of the underlying substrate on the air stability of on-surface synthesized nanostructures. Applying an on-surface synthesis approach, we report a similar behavior in the synthesis of 1D metal–organic nanostructures based on a BOPHY photoactive molecule on two coinage metal surfaces, Au(1 1 1) and Ag(1 1 1), but a distinct air stability of these nanostructures when exposed to the atmospheric pressure due to the different catalytic properties of the substrates. In both cases, important comparative conclusions are extracted thanks to a combination of surface science characterization techniques with theoretical calculations. This study opens a door to the synthesis of low-dimensional photoactive materials with potential applications, emphasizing the critical role of the substrate not only in the synthesis process but also in the air stability of on-surface synthesized nanostructures.