Orbital Mapping of Semiconducting Perylenes on Cu(111)

Giovanni Di Santo*, Tanja Miletić, Mathias Schwendt, Yating Zhou, Benson M. Kariuki, Kenneth D. M. Harris, Luca Floreano, Andrea Goldoni, Peter Puschnig, Luca Petaccia, Davide Bonifazi

J. Phys. Chem. C 2021, 125, 44, 24477–24486

DOI: 10.1021/acs.jpcc.1c05575


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.

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