Organic radical monolayers (r-MLs) bonded to metal surfaces are potential materials for the development of molecular (spin)electronics. Typically, stable radicals bearing surface anchoring groups are used to generate r-MLs.
Following a recent theoretical proposal based on a model system, we report the first experimental realization of a metal surface-induced r-ML, where a rationally chosen closed-shell precursor 3,5-dichloro-4-[bis(2,4,6-trichlorophenyl)methylen]cyclohexa-2,5-dien-1-one (1) transforms into a stable neutral open-shell species (1•) via chemisorption on the Ag(111) surface. X-ray photoelectron spectroscopy reveals that the >C═O group of 1 reacts with the surface, forming a C–O–Ag linkage that induces an electronic rearrangement that transforms 1 to 1•. We further show that surface reactivity is an important factor in this process whereby Au(111) is inert towards 1, whereas the Cu(111) surface leads to dehalogenation reactions. The radical nature of the Ag(111)-bound monolayer was further confirmed by angle-resolved photoelectron spectroscopy and electronic structure calculations, which provide evidence of the emergence of the singly occupied molecular orbital (SOMO) of 1•.
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Neutral Organic Radical Formation by Chemisorption on Metal Surfaces
M. R. Ajayakumar, César Moreno*, Isaac Alcón, Francesc Illas, Concepció Rovira, Jaume Veciana, Stefan T. Bromley*, Aitor Mugarza, and Marta Mas-Torrent*.