Well-ordered surface metal atoms complexation by deposition of Pd cyclometallated compounds on Ag (110)

by M. Stojkovska, D. Perilli, J. E. Barcelon, M. Smerieri, G. Carraro, T. H. Dinh, 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 2022, 606, pp 154960 View at Publisher
DOI: 10.1016/j.apsusc.2022.154960


In this paper we performed the deposition and self-assembly of a Pd-cyclometallated compound on Ag(110) surface for the first time. The system is investigated from the morphological and chemical point of view by scanning tunneling microscopy and x-ray photoemission spectroscopy, respectively, and the results are validated by ab-initio calculations. Our combined experimental and theoretical study aims at elucidating the atomistic details of the chemical steps following Pd cyclometallate deposition on the metallic substrate. To do that, we analyze the electronic and chemical properties of the species present on the surface at the end of the preparation process at room temperature and at 150 °C. We observe an unexpected complex chemistry: on one side, the organometallic molecules are found to dissociate into fragments, forming a well-ordered metal–carbon network; on the other side, Pd atoms become buried in the bulk of the metal substrate following metal exchange with surface Ag atoms. The details of this mechanistic study reveal the active role played by the metal substrate in promoting the chemistry of the deposited Pd cyclometallates and could open new perspectives for the application of this class of materials in heterogeneous catalysis.