Formation of diphenyl-bipyridine units by surface assisted cross coupling in Pd-cyclometalled complexes

by J. E. Barcelon, M. Stojkovska, D. Perilli, G. Carraro, M. Smerieri, L. Vattuone, M. Rocca, G, Bracco, M. Dell'Angela, R. Costantini, A. Cossaro, L. Vaghi, A. Papagni, C. Di Valentin and L. Savio
Applied Surface Science 2023, 609, pp 155307 View at Publisher
DOI: 10.1016/j.apsusc.2022.155307


The Pd cyclometallated complex [(5-bromo-2-phenylpyridine)Pd(μ-Cl)]2 is deposited on Ag(1 1 0) at room temperature by sublimation in ultra-high vacuum. The thermal evolution of the system is followed by scanning tunnelling microscopy and X-ray photoemission spectroscopy, while the initial and final configurations are validated by ab-initio calculations. We observe the surface induced dissociation of the molecule and the occurrence of a cross coupling reaction between the two organic fragments, leading to the surface assisted synthesis of diphenyl-bipyridine molecules. Such a process, occurring with low probability at RT, is thermally activated and competes with desorption. At variance with most cross-coupling reactions at surfaces reported in literature, in this case the reactants come from the dissociation of the same compound so that only one precursor is employed, leading to a simplified preparation protocol. The Br and Cl atoms dissociated from the molecule bind to the surface and promote an extended surface reconstruction upon annealing, which was not observed previously upon deposition of halogenated aromatic compounds.