Self-metalation of a free-base porphyrin on a metal oxide surface mediated by extended defects: Insight from ab initio molecular dynamics simulations

• DOI: 10.1016/j.susc.2022.122101
• Publication Date: 2022-04-20T18:30:12Z
• Authors: Osman Barış Malcı...; Michel Bockstedte
• Keywords: Metalation; Surface Modification

An important pathway for functionalization of porphyrin-based organic-inorganic structures is the metalation porphyrins. Recently, porphyrin was demonstrated on different metal oxide surfaces, however, underlying mechanisms regarding role surface morphology, substituted metal, and ligands are still under investigation. Here we address adsorption self-metalation H2TPP a MgO(001) with low-coordinated sites. We employ ab initio molecular dynamics simulations around room temperature to provide insight into dynamic steric effects. observe that mobile pristine as hindrance by phenyl rings prevents physisorption macrocycle at specific site. In contrast, step edges or kink sites anchor points exposing low-coordinated, reactive oxygen-sites hydrogens macrocycle. report spontaneous proton transfer these forming an intermediate complex before occurs. The energetics reaction modeled.