It is shown that the self-assembly of a surface-confined metal–organic network such as cobalt porphyrins on graphene is accompanied by the evolution of coordination-dependent observables in the electronic structure: variation of the layer’s valence states within almost 1 eV range and of the metal atoms oxidation states. Coordination of cobalt porphyrins, driven by Coad-atoms, allows the synthesis of single metal atom centers with +3, +2, or +1 oxidation states. The electronic structure is determined by lateral interactions extending up to a few nanometers, beyond nearest-neighbor distances. The reactivity of the single Co sites, which is strongly dependent on the local electronic configuration and, thus, on the metal-specific oxidation state, is probed by carbon monoxide, which is found to ligate at pyridinic Co(I) at room temperature for background pressures above a fraction of a mbar.
Co(III), Co(II), Co(I): Tuning Single Cobalt Metal Atom Oxidation States in a 2D Coordination Network
Armillotta, Francesco;Bidoggia, Davide;Baronio, Stefania;Costantini, Roberto;Cojocariu, Iulia;Morgante, Alberto;Peressi, Maria;Vesselli, Erik
2024-01-01
Abstract
It is shown that the self-assembly of a surface-confined metal–organic network such as cobalt porphyrins on graphene is accompanied by the evolution of coordination-dependent observables in the electronic structure: variation of the layer’s valence states within almost 1 eV range and of the metal atoms oxidation states. Coordination of cobalt porphyrins, driven by Coad-atoms, allows the synthesis of single metal atom centers with +3, +2, or +1 oxidation states. The electronic structure is determined by lateral interactions extending up to a few nanometers, beyond nearest-neighbor distances. The reactivity of the single Co sites, which is strongly dependent on the local electronic configuration and, thus, on the metal-specific oxidation state, is probed by carbon monoxide, which is found to ligate at pyridinic Co(I) at room temperature for background pressures above a fraction of a mbar.File | Dimensione | Formato | |
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Adv Funct Materials - 2024 - Armillotta - Co III Co II Co I Tuning Single Cobalt Metal Atom Oxidation States in a 2D.pdf
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adfm202408200-sup-0001-suppmat.pdf
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