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Orbital mapping of semiconducting perylenes on Cu(111)

Di Santo, Giovanni, Miletic, Tanja, Schwendt, Mathias, Zhou, Yating, Kariuki, Benson M., Harris, Kenneth D. M., Floreano, Luca, Goldoni, Andrea, Puschnig, Peter, Petaccia, Luca and Bonifazi, Davide 2021. Orbital mapping of semiconducting perylenes on Cu(111). Journal of Physical Chemistry C 125 (44) , 24477–24486. 10.1021/acs.jpcc.1c05575

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Semiconducting O-doped polycyclic aromatic hydrocarbons constitute a class of molecules whose optoelectronic properties can be tailored by acting on the π-extension of the carbon-based frameworks and on the oxygen linkages. Although much is known about their photophysical and electrochemical properties in solution, their self-assembly interfacial behavior on solid substrates has remained unexplored so far. In this paper, we have focused our attention on the on-surface self-assembly of O-doped bi-perylene derivatives. Their ability to assemble in ordered networks on Cu(111) single-crystalline surfaces allowed a combination of structural, morphological, and spectroscopic studies. In particular, the exploitation of the orbital mapping methodology based on angle-resolved photoemission spectroscopy, with the support of scanning tunneling microscopy and low-energy electron diffraction, allowed the identification of both the electronic structure of the adsorbates and their geometric arrangement. Our multi-technique experimental investigation includes the structure determination from powder X-ray diffraction data for a specific compound and demonstrates that the electronic structure of such large molecular self-assembled networks can be studied using the reconstruction methods of molecular orbitals from photoemission data even in the presence of segregated chiral domains.

Item Type: Article
Date Type: Publication
Status: Published
Schools: Chemistry
Publisher: American Chemical Society
ISSN: 1932-7447
Funders: EU Horizon 2020
Date of First Compliant Deposit: 8 November 2021
Date of Acceptance: 5 October 2021
Last Modified: 15 Nov 2021 11:15

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