On-Surface Chemistry: Probing the Presence of Adatoms on Differently Terminated Surfaces by Porphyrin Metalation

Reactive adsorbates in on-surface reactions and in heterogeneous catalysis on different substrates are of emerging importance. This is for the crucial roles they take in reaction pathways and for their decisive influence on reaction kinetics. 1 The thermally activated 2D mobility 2 of reaction precursors and reactive adatoms as well as their spatial and temporal coincidence at reaction sites is of mechanistic importance for many interface-specific reactions. In our work, we use the well-studied metalation reaction of H 2 -porphyrins to investigate the action of adatoms on metallic and passivated surface substrates. Porphyrin metalation has been established on atomically clean metallic substrates 3 as well as on metal-oxides 4 and metallic surfaces modified by oxygen 5. We perform spectro-microscopy correlation experiments combining X-ray Photoelectron Spectroscopy, Ultraviolet Photoelectron Spectroscopy, Low Energy Electron Diffraction and Scanning Tunnelling Microscopy on Cl- and N terminated Cu(001). Thereby we find extended layers of adsorbate-induced superstructures that have decisive and contrasting impact on the reactivity of the surface, as well as on molecular self-assembly. The O and N termination of Cu facilitates the metalation reaction and self-assembled domains of CuTPP are formed at room temperature. Cl termination on the contrary, fully inhibits the metalation reaction and causes 2HTPP to assemble into small ‘magic’ clusters. References 1 Waiz et al., Nature 541, 68–71 (2017). 10.1038/nature20782 2 Ahsan et al., Nanoscale, 2019, 11, 4895. 10.1021/acs.jpcc.3c03325 3 Auwärter et al., ChemPhysChem 8 , 250 (2007). 10.1002/cphc.200600675 4 Wang, C. et al Chem Commun 50 , 8291 (2014). 10.1039/C4CC02919D 5 Nowakowski et al., Chem. Commun. , 49 , 2347 (2013). 10.1039/c3cc39134e 6 Nowakowski et al., ChemistrySelect 2016, 5, 891 –895. 10.1002/slct.201600215 Figure 1