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Orbital mapping of semiconducting perylenes on Cu(111)

Di Santo, Giovanni, Miletic, Tanja, Schwendt, Mathias, Zhou, Yating, Kariuki, Benson M. ORCID: https://orcid.org/0000-0002-8658-3897, Harris, Kenneth D. M. ORCID: https://orcid.org/0000-0001-7855-8598, Floreano, Luca, Goldoni, Andrea, Puschnig, Peter, Petaccia, Luca and Bonifazi, Davide ORCID: https://orcid.org/0000-0001-5717-0121 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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Abstract

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: 10 Nov 2022 10:00
URI: https://orca.cardiff.ac.uk/id/eprint/145365

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