Catalytic effects of iron adatoms in poly(para-phenylene) synthesis on rutile TiO2(110)†

n-Armchair graphene nanoribbons (nAGNRs) are promising components for next-generation nanoelectronics due to their controllable band gap, which depends on their width and edge structure. Using non-metal surfaces for fabricating nAGNRs gives access to reliable information on their electronic properties. We investigated the influence of light and iron adatoms on the debromination of 4,4′′-dibromo-p-terphenyl precursors affording poly(para-phenylene) (PPP as the narrowest GNR) wires through the Ullmann coupling reaction on a rutile TiO₂(110) surface, which we studied by scanning tunneling microscopy and X-ray photoemission spectroscopy. The temperature threshold for bromine bond cleavage and desorption is reduced upon exposure to UV light (240–395 nm wavelength), but the reaction yield could not be improved. However, in the presence of codeposited iron adatoms, precursor debromination occurred even at 77 K, allowing for Ullmann coupling and PPP wire formation at 300–400 K, i.e., markedly lower temperatures compared to the conditions without iron adatoms. Furthermore, scanning tunneling spectroscopy data reveal that adsorbed PPP wires feature a band gap of ≈3.1 eV.