Redox-Addressable Single-Molecule Junctions Incorporating a Persistent Organic Radical

Angew Chem Int Ed Engl. 2022 Jun 7;61(23):e202116985. doi: 10.1002/anie.202116985. Epub 2022 Apr 5.

Abstract

Integrating radical (open-shell) species into non-cryogenic nanodevices is key to unlocking the potential of molecular electronics. While many efforts have been devoted to this issue, in the absence of a chemical/electrochemical potential the open-shell character is generally lost in contact with the metallic electrodes. Herein, single-molecule devices incorporating a 6-oxo-verdazyl persistent radical have been fabricated using break-junction techniques. The open-shell character is retained at room temperature, and electrochemical gating permits in situ reduction to a closed-shell anionic state in a single-molecule transistor configuration. Furthermore, electronically driven rectification arises from bias-dependent alignment of the open-shell resonances. The integration of radical character, transistor-like switching, and rectification in a single molecular component paves the way to further studies of the electronic, magnetic, and thermoelectric properties of open-shell species.

Keywords: Molecular Devices; Molecular Electronics; Radicals.