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

doi:10.1021/acsnano.7b00766

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 journal › Article › peer-review

23 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 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
State	Published - 28 Mar 2017
Externally published	Yes

Keywords

corrole
cyclization
defluorination
network
radical cascade reactions
regioselectivity
surface

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10.1021/acsnano.7b00766

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Tebi, S., Paszkiewicz, M., Aldahhak, H., Allegretti, F., Gonglach, S., Haas, M., Waser, M., Deimel, P. S., Aguilar, P. C., 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

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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 conjugated corrole system.",

keywords = "corrole, cyclization, defluorination, network, radical cascade reactions, regioselectivity, surface",

author = "Stefano Tebi and Mateusz Paszkiewicz and Hazem Aldahhak and Francesco Allegretti and Sabrina Gonglach and Michael Haas and Mario Waser and Deimel, {Peter S.} and Aguilar, {Pablo Casado} and Zhang, {Yi Qi} and Papageorgiou, {Anthoula C.} and Duncan, {David A.} and Barth, {Johannes V.} and Schmidt, {Wolf G.} and Reinhold Koch and Uwe Gerstmann and Eva Rauls and Florian Klappenberger and Wolfgang Sch{\"o}fberger and Stefan M{\"u}llegger",

note = "Publisher Copyright: {\textcopyright} 2017 American Chemical Society.",

year = "2017",

month = mar,

day = "28",

doi = "10.1021/acsnano.7b00766",

language = "English",

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Tebi, S, Paszkiewicz, M, Aldahhak, H, Allegretti, F, Gonglach, S, Haas, M, Waser, M, Deimel, PS, Aguilar, PC, Zhang, YQ, 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, Mateusz

AU - Aldahhak, Hazem

AU - Allegretti, Francesco

AU - Gonglach, Sabrina

AU - Haas, Michael

AU - Waser, Mario

AU - Deimel, Peter S.

AU - Aguilar, Pablo Casado

AU - Zhang, Yi Qi

AU - Papageorgiou, Anthoula C.

AU - Duncan, David A.

AU - Barth, Johannes V.

AU - Schmidt, Wolf G.

AU - Koch, Reinhold

AU - Gerstmann, Uwe

AU - Rauls, Eva

AU - Klappenberger, Florian

AU - Schöfberger, Wolfgang

AU - Müllegger, Stefan

PY - 2017/3/28

Y1 - 2017/3/28

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 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 conjugated corrole system.

KW - corrole

KW - cyclization

KW - defluorination

KW - network

KW - radical cascade reactions

KW - regioselectivity

KW - surface

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U2 - 10.1021/acsnano.7b00766

DO - 10.1021/acsnano.7b00766

M3 - Article

C2 - 28212484

AN - SCOPUS:85016492701

SN - 1936-0851

VL - 11

SP - 3383

EP - 3391

JO - ACS Nano

JF - ACS Nano

IS - 3

ER -

On-Surface Site-Selective Cyclization of Corrole Radicals

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Keywords

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