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

作者信息

Stefani Andrea, Bogdan Alexandra, Pop Flavia, Tassinari Francesco, Pasquali Luca, Fontanesi Claudio, Avarvari Narcis

机构信息

Department of Physics, (FIM), University of Modena, Via Campi 213/A, 41125 Modena, Italy.

University of Angers, CNRS, MOLTECH-Anjou, SFR MATRIX, F-49000 Angers, France.

出版信息

J Chem Phys. 2023 Nov 28;159(20). doi: 10.1063/5.0171831.

DOI:10.1063/5.0171831
PMID:38014785
Abstract

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%.

摘要

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