Spin-dependent electrochemistry and electrochemical enantioselective recognition with chiral methylated bis(ethylenedithio)-tetrathiafulvalenes

Enantio-discrimination and spin-dependent electrochemistry (SDE), as a manifestation of the chirality-induced spin selectivity (CISS) effect, are important phenomena that can be probed by chiral electrochemistry. Here, we prepared chiralized surfaces of gold and nickel, to serve as working electrodes, through effective chemisorption of enantiopure dimethyl-bis(ethylenedithio)-tetrathiafulvalene (DM-BEDT-TTF) 1, tetramethyl-bis(ethylenedithio)-tetrathiafulvalene (TM-BEDT-TTF) 2, and their capped silver nanoparticle (AgNPs) aggregate by simple incubation of the metallic substrates. The effective chemisorption was checked by means of ultrahigh vacuum x-ray photoelectron spectroscopy (XPS) and by electro-desorption experiments, i.e., cyclic voltammetry (CV) scans showing a first electro-desorption peak at about -1.0 V. The Au|1 and Au|2 chiral electrodes were successfully used in CV experiments exploiting chiral redox probes. Finally, the hybrid interfaces Ni|enantiopure 1 or 2|AgNPs served as working electrodes in SDE experiments. In particular, the hybrid chiral interfaces Ni|(R)-2|AgNPs and Ni|(S)-2|AgNPs exhibited a significant spin-filtering ability, as a manifestation of the CISS effect, with average spin polarization values of 15%.

Automated summary

The article investigates the important phenomena of enantio-discrimination and spin-dependent electrochemistry through chiral electrochemistry. Chiralized surfaces of gold and nickel were prepared via effective chemisorption and used as working electrodes. The results show significant manifestation of chirality-induced spin selectivity effect in cyclic voltammetry and spin-dependent electrochemistry experiments.