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Kekulene: On-Surface Synthesis, Orbital Structure, and Aromatic Stabilization

preprint
submitted on 06.08.2020 and posted on 07.08.2020 by Anja Haags, Alexander Reichmann, Qitang Fan, Larissa Egger, Hans Kirschner, Tim Naumann, Simon Werner, Tobias Vollgraff, Jörg Sundermeyer, Lukas Eschmann, Xiaosheng Yang, Dominik Brandstetter, François C. Bocquet, Georg Koller, Alexander Gottwald, Mathias Richter, Michael G. Ramsey, Michael Rohlfing, Peter Puschnig, Michael Gottfried, Serguei Soubatch, F. Stefan Tautz
We revisit the question of kekulene’s aromaticity by focusing on the electronic structure of its frontier orbitals as determined by angle-resolved photoemission spectroscopy. To this end, we have developed a specially designed precursor, 1,4,7(2,7)-triphenanthrenacyclononaphane-2,5,8-triene, which allows us to prepare sufficient quantities of kekulene of high purity directly on a Cu(111) surface, as confirmed by scanning tunneling microscopy. Supported by density functional calculations, we determine the orbital structure of kekulene’s highest occupied molecular orbital by photoelectron tomography. In agreement with a recent aromaticity assessment of kekulene based solely on C–C bond lengths, we conclude that the π-conjugation of kekulene is better described by the Clar model rather than a superaromatic model. Thus, by exploiting the capabilities of photoemission tomography, we shed light on the question which consequences aromaticity holds for the frontier electronic structure of a π-conjugated molecule.

Funding

SFB 1083:  Structure and Dynamics of Internal Interfaces

Deutsche Forschungsgemeinschaft

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Austrian Science Fund (FWF) (projects P27649-N20, P27427-N20, and I3731)

Deutsche Forschungsgemeinschaft (DFG), projects Po 2226/2- 1, Ri 804/8-1, Go 1812/2-1

History

Email Address of Submitting Author

qitang.fan@uni-marburg.de

Institution

University of Marburg

Country

Germany

ORCID For Submitting Author

0000-0002-2629-6212

Declaration of Conflict of Interest

The authors declare no conflict of interest

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