On-Surface Site-Selective Cyclization of Corrole Radicals

Stefano Tebi; M. Paszkiewicz; Hazem Aldahhak; F. Allegretti; Sabrina Gonglach; Michael Haas; Mario Waser; P. S. Deimel; P. Casado Aguilar; Y.-Q. Zhang; A. C. Papageorgiou; D. A. Duncan; Johannes V. Barth; Wolf Gero Schmidt; Reinhold Koch; Uwe Gerstmann; Eva Rauls; F. Klappenberger; Wolfgang Schöfberger; Stefan Müllegger

doi:10.1021/acsnano.7b00766

Research output: Contribution to journal › Article › peer-review

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.

Original language	English
Pages (from-to)	3383−3391
Number of pages	9
Journal	ACS Nano
Volume	11
Issue number	3
DOIs	https://doi.org/10.1021/acsnano.7b00766
Publication status	Published - 2017

Fields of science

210006 Nanotechnology
103 Physics, Astronomy
103011 Semiconductor physics
103018 Materials physics
202032 Photovoltaics
103009 Solid state physics
103017 Magnetism

JKU Focus areas

Engineering and Natural Sciences (in general)

Access to Document

10.1021/acsnano.7b00766

Cite this

Tebi, S., Paszkiewicz, M., Aldahhak, H., Allegretti, F., Gonglach, S., Haas, M., Waser, M., Deimel, P. S., Casado Aguilar, P., Zhang, Y.-Q., Papageorgiou, A. C., Duncan, D. A., Barth, J. V., Schmidt, W. G., Koch, R., Gerstmann, U., Rauls, E., Klappenberger, F., Schöfberger, W., & Müllegger, S. (2017). On-Surface Site-Selective Cyclization of Corrole Radicals. ACS Nano, 11(3), 3383−3391. https://doi.org/10.1021/acsnano.7b00766

@article{a82a5a3ccf7544519aa5bdc74bbc9c07,

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.",

author = "Stefano Tebi and M. Paszkiewicz and Hazem Aldahhak and F. Allegretti and Sabrina Gonglach and Michael Haas and Mario Waser and Deimel, \{P. S.\} and \{Casado Aguilar\}, P. and Y.-Q. Zhang and Papageorgiou, \{A. C.\} and Duncan, \{D. A.\} and Barth, \{Johannes V.\} and Schmidt, \{Wolf Gero\} and Reinhold Koch and Uwe Gerstmann and Eva Rauls and F. Klappenberger and Wolfgang Sch{\"o}fberger and Stefan M{\"u}llegger",

year = "2017",

doi = "10.1021/acsnano.7b00766",

language = "English",

volume = "11",

pages = "3383−3391",

journal = "ACS Nano",

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Tebi, S, Paszkiewicz, M, Aldahhak, H, Allegretti, F, Gonglach, S, Haas, M, Waser, M, Deimel, PS, Casado Aguilar, P, Zhang, Y-Q, Papageorgiou, AC, Duncan, DA, Barth, JV, Schmidt, WG, Koch, R, Gerstmann, U, Rauls, E, Klappenberger, F, Schöfberger, W & Müllegger, S 2017, 'On-Surface Site-Selective Cyclization of Corrole Radicals', ACS Nano, vol. 11, no. 3, pp. 3383−3391. https://doi.org/10.1021/acsnano.7b00766

TY - JOUR

T1 - On-Surface Site-Selective Cyclization of Corrole Radicals

AU - Tebi, Stefano

AU - Paszkiewicz, M.

AU - Aldahhak, Hazem

AU - Allegretti, F.

AU - Gonglach, Sabrina

AU - Haas, Michael

AU - Waser, Mario

AU - Deimel, P. S.

AU - Casado Aguilar, P.

AU - Zhang, Y.-Q.

AU - Papageorgiou, A. C.

AU - Duncan, D. A.

AU - Barth, Johannes V.

AU - Schmidt, Wolf Gero

AU - Koch, Reinhold

AU - Gerstmann, Uwe

AU - Rauls, Eva

AU - Klappenberger, F.

AU - Schöfberger, Wolfgang

AU - Müllegger, Stefan

PY - 2017

Y1 - 2017

N2 - 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.

AB - 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.

UR - https://www.scopus.com/pages/publications/85016492701

U2 - 10.1021/acsnano.7b00766

DO - 10.1021/acsnano.7b00766

M3 - Article

SN - 1936-0851

VL - 11

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JO - ACS Nano

JF - ACS Nano

IS - 3