title: On-Surface Site-Selective Cyclization of Corrole Radicals.
abstract: Radical cyclization is among the most powerful and versatile reactions for constructing mono- and polycyclic systems, but has, to date, remained unexplored in the context of on-surface synthesis. We report the controlled on-surface synthesis of stable corrole radicals on Ag(111) via site-specific dehydrogenation of a pyrrole N-H bond in the 5,10,15-tris(pentafluoro-phenyl)-corrole triggered by annealing at 330 K under ultrahigh-vacuum conditions. We reveal a thermally induced regioselective cyclization reaction mediated by a radical cascade and resolve the reaction mechanism of the pertaining cyclodefluorination reaction at the single-molecule level. Via intramolecularly resolved probing of the radical-related Kondo signature, we achieve real space visualization of the distribution of the unpaired electron density over specific sites within the corrole radical. Annealing to 550 K initiates intermolecular coupling reactions, producing an extended π-conjugated corrole system.
authors.forename: Stefano
authors.initials: S
authors.lastname: Tebi
authors.affiliation: Physics Department E20, Technical University of Munich , James-Franck Straße 1, 85748 Garching, Germany.
authors.forename: Mateusz
authors.initials: M
authors.lastname: Paszkiewicz
authors.affiliation: Physics Department, Paderborn University , Warburger Straße 100, 33098 Paderborn, Germany.
authors.forename: Hazem
authors.initials: H
authors.lastname: Aldahhak
authors.affiliation: Physics Department E20, Technical University of Munich , James-Franck Straße 1, 85748 Garching, Germany.
authors.forename: Francesco
authors.initials: F
authors.lastname: Allegretti
authors.forename: Sabrina
authors.initials: S
authors.lastname: Gonglach
authors.forename: Michael
authors.initials: M
authors.lastname: Haas
authors.forename: Mario
authors.identifier: 0000-0002-8421-8642
authors.initials: M
authors.lastname: Waser
authors.affiliation: Physics Department E20, Technical University of Munich , James-Franck Straße 1, 85748 Garching, Germany.
authors.forename: Peter S
authors.initials: PS
authors.lastname: Deimel
authors.affiliation: Physics Department E20, Technical University of Munich , James-Franck Straße 1, 85748 Garching, Germany.
authors.forename: Pablo Casado
authors.initials: PC
authors.lastname: Aguilar
authors.affiliation: Physics Department E20, Technical University of Munich , James-Franck Straße 1, 85748 Garching, Germany.
authors.forename: Yi-Qi
authors.initials: YQ
authors.lastname: Zhang
authors.affiliation: Physics Department E20, Technical University of Munich , James-Franck Straße 1, 85748 Garching, Germany.
authors.forename: Anthoula C
authors.identifier: 0000-0003-1054-0097
authors.initials: AC
authors.lastname: Papageorgiou
authors.affiliation: Physics Department E20, Technical University of Munich , James-Franck Straße 1, 85748 Garching, Germany.
authors.forename: David A
authors.initials: DA
authors.lastname: Duncan
authors.affiliation: Physics Department E20, Technical University of Munich , James-Franck Straße 1, 85748 Garching, Germany.
authors.forename: Johannes V
authors.initials: JV
authors.lastname: Barth
authors.affiliation: Physics Department, Paderborn University , Warburger Straße 100, 33098 Paderborn, Germany.
authors.forename: Wolf G
authors.initials: WG
authors.lastname: Schmidt
authors.forename: Reinhold
authors.initials: R
authors.lastname: Koch
authors.affiliation: Physics Department, Paderborn University , Warburger Straße 100, 33098 Paderborn, Germany.
authors.forename: Uwe
authors.initials: U
authors.lastname: Gerstmann
authors.affiliation: Physics Department, Paderborn University , Warburger Straße 100, 33098 Paderborn, Germany.
authors.forename: Eva
authors.initials: E
authors.lastname: Rauls
authors.affiliation: Physics Department E20, Technical University of Munich , James-Franck Straße 1, 85748 Garching, Germany.
authors.forename: Florian
authors.identifier: 0000-0002-2877-6105
authors.initials: F
authors.lastname: Klappenberger
authors.forename: Wolfgang
authors.identifier: 0000-0002-8055-8906
authors.initials: W
authors.lastname: Schöfberger
authors.forename: Stefan
authors.initials: S
authors.lastname: Müllegger
keywords: corrole; cyclization; defluorination; network; radical cascade reactions; regioselectivity; surface