Self‐metalation of porphyrins at the solid‐gas interface

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