On-Surface Site-Selective Cyclization of Corrole Radicals

Stefano Tebi, Mateusz Paszkiewicz, Hazem Aldahhak, Francesco Allegretti, Sabrina Gonglach, Michael Haas, Mario Waser, Peter S. Deimel, Pablo Casado Aguilar, Yi Qi Zhang, Anthoula C. Papageorgiou, David A. Duncan, Johannes V. Barth, Wolf G. Schmidt, Reinhold Koch, Uwe Gerstmann, Eva Rauls, Florian Klappenberger, Wolfgang Schöfberger, Stefan Müllegger

Research output: Contribution to journalArticlepeer-review

22 Scopus citations

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 conjugated corrole system.

Original languageEnglish
Pages (from-to)3383-3391
Number of pages9
JournalACS Nano
Volume11
Issue number3
DOIs
StatePublished - 28 Mar 2017
Externally publishedYes

Keywords

  • corrole
  • cyclization
  • defluorination
  • network
  • radical cascade reactions
  • regioselectivity
  • surface

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