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Funding provided by the Austrian Science Fund (FWF) via D-A-CH i958 "High-Valent Metal Tetrapyrroles for Surface Supported Catalysis" and "Oxygen and Hydrogen Evolution Triggered by Surface-Supported Catalysts" P28167-N34, the European Union via ERC advanced grant MolArt (grant 247299), the German Research Foundation (DFG) via KL 2294/3-1, FOR-1405, GRK 1464, and the Munich-Center for Advanced Photonics (MAP) is gratefully acknowledged. Computational resources were allocated at the HLRS Stuttgart and the Paderborn Center for Parallel Computing (PC²). We also thank the Helmholtz-Zentrum, Berlin, for the allocation of synchrotron radiation beamtime and for financial support. We thank Peter Feulner for his support in setting up the XPS-TPD chamber in Bessy II (Berlin) and in our on-campus laboratory (TUM-Garching) and for fruitful discussion during the measurements. The NMR spectrometers were acquired in collaboration with the University of South Bohemia (CZ) with financial support from the European Union through the EFRE INTERREG IV ETC-AT-CZ program (project M00146, "RERI-uasb").

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On-Surface Site-Selective Cyclization of Corrole Radicals

Publicated to:ACS Nano. 11 (3): 3383-3391 - 2017-03-01 11(3), DOI: 10.1021/acsnano.7b00766

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

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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 cyclo-defluorination 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 pi-conjugated corrole system.

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