Resolving the Unpaired-Electron Orbital Distribution in a Stable Organic Radical by Kondo Resonance Mapping

Angew Chem Int Ed Engl. 2019 Aug 5;58(32):11063-11067. doi: 10.1002/anie.201904851. Epub 2019 Jun 28.

Abstract

The adsorption geometry and the electronic structure of a Blatter radical derivative on a gold surface were investigated by a combination of high-resolution noncontact atomic force microscopy and scanning tunneling microscopy. While the hybridization with the substrate hinders direct access to the molecular states, we show that the unpaired-electron orbital can be probed with Ångström resolution by mapping the spatial distribution of the Kondo resonance. The Blatter derivative features a peculiar delocalization of the unpaired-electron orbital over some but not all moieties of the molecule, such that the Kondo signature can be related to the spatial fingerprint of the orbital. We observe a direct correspondence between these two quantities, including a pronounced nodal plane structure. Finally, we demonstrate that the spatial signature of the Kondo resonance also persists upon noncovalent dimerization of molecules.

Keywords: atomic force microscopy; molecular electronics; radicals; scanning tunneling microscopy; single-molecule studies.