journal article·2023-12-26Open access

Noncontact Layer Stabilization of Azafullerene Radicals: Route toward High-Spin-Density Surfaces

Yuri Tanuma, Gregor Kladnik, Luca Schio, Marion van Midden Mavrič, Bastien Anézo, Erik Zupanič, Gregor Bavdek, Ruben Canton-Vitoria, Luca Floreano, Nikos Tagmatarchis, Hermann A. Wegner, Alberto Morgante, Christopher P. Ewels, Dean Cvetko, Denis Arčon

ACS Nano· Volume 17· Issue 24

Abstract

High Resolution Image Download MS PowerPoint Slide We deposit azafullerene C 59 N • radicals in a vacuum on the Au(111) surface for layer thicknesses between 0.35 and 2.1 monolayers (ML). The layers are characterized using X-ray photoemission (XPS) and X-ray absorption fine structure (NEXAFS) spectroscopy, low-temperature scanning tunneling microscopy (STM), and by density functional calculations (DFT). The singly unoccupied C 59 N orbital (SUMO) has been identified in the N 1s NEXAFS/XPS spectra of C 59 N layers as a spectroscopic fingerprint of the molecular radical state. At low molecular coverages (up to 1 ML), films of monomeric C 59 N are stabilized with the nonbonded carbon orbital neighboring the nitrogen oriented toward the Au substrate, whereas in-plane intermolecular coupling into diamagnetic (C 59 N) 2 dimers takes over toward the completion of the second layer. By following the C 59 N • SUMO peak intensity with increasing molecular coverage, we identify an intermediate high-spin-density phase between 1 and 2 ML, where uncoupled C 59 N • monomers in the second layer with pronounced radical character are formed. We argue that the C 59 N • radical stabilization of this supramonolayer phase of monomers is achieved by suppressed coupling to the substrate. This results from molecular isolation on top of the passivating azafullerene contact layer, which can be explored for molecular radical state stabilization and positioning on solid substrates.
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Research context

OpenAlex topics: Fullerene Chemistry and Applications · Advanced Chemical Physics Studies · Graphene research and applications

SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.

Affiliations

Jožef Stefan Institute, Jamova 39, SI-1000 Ljubljana, Slovenia

Center for Advanced Research of Energy and Materials (CAREM), Hokkaido University, Kita 13, Nishi 8, Kitaku, Sapporo 060-8628, Japan

Faculty of Mathematics and Physics, University of Ljubljana, Jadranska 19, SI-1000 Ljubljana, Slovenia

CNR-IOM, Istituto Officina dei Materiali, Basovizza Area Science Park, 34149 Trieste, Italy

Institut des Matériaux de Nantes Jean Rouxel (IMN), UMR 6502 CNRS, Nantes University, 44322 Nantes, France

Faculty of Education, University of Ljubljana, Kardeljeva ploščad 16, SI-1000 Ljubljana Slovenia

Theoretical and Physical Chemistry Institute, National Hellenic Research Foundation, 48 Vassileos Constantinou Avenue, Athens 11635, Greece

Institute of Organic Chemistry, Justus Liebig University Giessen, Heinrich-Buff-Ring 17, 35392 Giessen, Germany

Center for Materials Research (ZfM/LaMa), Justus Liebig University Giessen, Heinrich-Buff-Ring 16, 35392 Giessen, Germany

Physics Department, University of Trieste, Via Valerio 2, 34012 Trieste, Italy

Funding

Minist?re de l'Enseignement sup?rieur, de la Recherche et de l'Innovation · Agence Nationale de la Recherche · Hokkaido University · Javna Agencija za Raziskovalno Dejavnost RS · Campus France · European Commission · Japan Society for the Promotion of Science · European Cooperation in Science and Technology · Minist?re de l'Europe et des Affaires ?trang?res

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