Self‐Metalation of Porphyrins at the Solid–Gas Interface

Self‐metalation is a promising route to include a single metal atom in a tetrapyrrolic macrocycle in organic frameworks supported by metal surfaces. The molecule–surface interaction may provide the charge transfer and the geometric distortion of the molecular plane necessary for metal inclusion. However, at a metal surface the presence of an activation barrier can represent an obstacle that cannot be compensated by a higher substrate temperature without affecting the layer integrity. The formation of the intermediate state can be facilitated in some cases by oxygen pre‐adsorption at the supporting metal surface, like in the case of 2H‐TPP/Pd(100). In such cases, the activation barrier can be overcome by mild annealing, yielding the formation of desorbing products and of the metalated tetrapyrrole. We show here that the self‐metalation of 2H‐TPP at the Pd(100) surface can be promoted already at room temperature by the presence of an oxygen gas phase at close‐to‐ambient conditions via an Eley–Rideal mechanism.