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A Systematic Study of Methyl Carbodithioate Esters as Effective Gold Contact Groups for Single-Molecule Electronics

Title: A Systematic Study of Methyl Carbodithioate Esters as Effective Gold Contact Groups for Single-Molecule Electronics
Authors: Ward, JS; Vezzoli, A; Wells, C; Bailey, S; Jarvis, SP; Lambert, CJ; Robertson, C; Nichols, RJ; Higgins, SJ
Publisher Information: Wiley
Publication Year: 2024
Collection: The University of Liverpool Repository
Description: There are several binding groups used within molecular electronics for anchoring molecules to metal electrodes (e.g., R−SMe, R−NH 2 , R−CS 2 − , R−S − ). However, some anchoring groups that bind strongly to electrodes have poor/unknown stability, some have weak electrode coupling, while for some their binding motifs are not well defined. Further binding groups are required to aid molecular design and to achieve a suitable balance in performance across a range of properties. We present an in-depth investigation into the use of carbodithioate esters as contact groups for single-molecule conductance measurements, using scanning tunnelling microscopy break junction measurements (STM-BJ) and detailed surface spectroscopic analysis. We demonstrate that the methyl carbodithioate ester acts as an effective contact for gold electrodes in STM-BJ measurements. Surface enhanced Raman measurements demonstrate that the C=S functionality remains intact when adsorbed on to gold nanoparticles. A gold(I) complex was also synthesised showing a stable C=S→Au I interaction from the ester. Comparison with a benzyl thiomethyl ether demonstrates that the C=S moiety significantly contributes to charge transport in single-molecule junctions. The overall performance of the CS 2 Me group demonstrates it should be used more extensively and has strong potential for the fabrication of larger area devices with long-term stability.
Document Type: article in journal/newspaper
File Description: text
Language: English
ISSN: 1433-7851
Relation: https://livrepository.liverpool.ac.uk/3181852/1/Angew%20Chem%20Int%20Ed%20-%202024%20-%20Ward%20-%20A%20Systematic%20Study%20of%20Methyl%20Carbodithioate%20Esters%20as%20Effective%20Gold%20Contact%20Groups%20for%281%29.pdf; Ward, JS orcid:0000-0002-4985-8572 , Vezzoli, A orcid:0000-0002-8059-0113 , Wells, C, Bailey, S orcid:0009-0005-0384-8810 , Jarvis, SP orcid:0000-0003-4031-1519 , Lambert, CJ orcid:0000-0003-2332-9610 , Robertson, C orcid:0000-0002-4789-7607 , Nichols, RJ orcid:0000-0002-1446-8275 and Higgins, SJ orcid:0000-0003-3518-9061 (2024) A Systematic Study of Methyl Carbodithioate Esters as Effective Gold Contact Groups for Single-Molecule Electronics Angewandte Chemie International Edition, 63 (31). e202403577-. ISSN 1433-7851, 1521-3773
DOI: 10.1002/anie.202403577
Availability: https://livrepository.liverpool.ac.uk/3181852/; https://doi.org/10.1002/anie.202403577
Rights: cc_by_4
Accession Number: edsbas.83428BAB
Database: BASE