Porphyrin metalation providing an example of a redox reaction facilitated by a surface reconstruction.

The presence of an oxygen reconstruction on the Cu(001) surface results in the self-metalation of 5,10,15,20-tetraphenylporphyrin (2HTPP) below room temperature (at ~285 K), in contrast to 2HTPP on the bare Cu(001) substrate, where a temperature of ~450 K is required. This study demonstrates the decisive impact of a surface reconstruction on the redox reaction in the solvent-free ultra-high vacuum environment.