On-Surface Synthesis and Characterization of Super-nonazethrene

Beginning with the early work of Clar et al. in 1955, zethrenes and their laterally extended homologues, super-zethrenes, have been intensively studied in the solution phase and widely investigated as optical and charge transport materials. Super­zethrenes are also considered to exhibit an open-shel...

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Bibliographic Details
Published in:The journal of physical chemistry letters 2021-09, Vol.12 (34), p.8314-8319
Main Authors: Turco, Elia, Mishra, Shantanu, Melidonie, Jason, Eimre, Kristjan, Obermann, Sebastian, Pignedoli, Carlo A, Fasel, Roman, Feng, Xinliang, Ruffieux, Pascal
Format: Article
Language:English
Subjects:
Physical Insights into Materials and Molecular Properties
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Summary:Beginning with the early work of Clar et al. in 1955, zethrenes and their laterally extended homologues, super-zethrenes, have been intensively studied in the solution phase and widely investigated as optical and charge transport materials. Super­zethrenes are also considered to exhibit an open-shell ground state and may thus serve as model compounds to investigate nanoscale π-magnetism. However, their synthesis is extremely challenging due to their high reactivity. We report here the on-surface synthesis of the hitherto largest zethrene homologuesuper-nona­zethreneon Au(111). Using single-molecule scanning tunneling microscopy and spectroscopy, we show that super-nona­zethrene exhibits an open-shell singlet ground state featuring a large spin polarization-driven electronic gap of 1 eV. Consistent with the emergence of an open-shell ground state, high-resolution tunneling spectroscopy reveals singlet–triplet spin excitations in super-nona­zethrene, characterized by a strong intra­molecular magnetic exchange coupling of 51 meV. Given the paucity of zethrene chemistry on surfaces, our results therefore provide unprecedented access to large, open-shell zethrene compounds amenable to scanning probe measurements, with potential application in molecular spintronics.
ISSN:1948-7185
1948-7185
DOI:10.1021/acs.jpclett.1c02381