Year: 2025
Type: article
Abstract: High Resolution Image Download MS PowerPoint Slide Recent studies have found that “chemically inert” gold surfaces may drive S–C( sp 3 ) bond cleavage reactions in thioether (−SR) linker groups, providing access to single-molecule junctions with chemisorbed Au–S contacts following the elimination of R + . Here, we demonstrate that such transformations occur more readily at elevated temperatures, rough surfaces, and in nonpolar solvents. We further show that a greater proportion of chemisorbed bonds are formed when R = −CPh 3 or −C 7 H 7 than when R = − t Bu, consistent with the relative stability of [ t Bu] + < [CPh 3 ] + ∼ [C 7 H 7 ] + carbocations. Our contact chemistry assignments are supported by first-principles transmission calculations, and we apply potential energy calculations to expose the relatively small influence of applied external electric fields on this bond breaking process. Together, this work provides a deeper understanding of reactivity at metal surfaces, of broad relevance to heterogeneous catalysis and critical to the stability and function of molecular junctions and monolayers.
Source: Nano Letters
Authors: Jazmine Prana, Luana Zagami, Kelly Yan, Daniel Hernangómez-Pérez, María Camarasa-Gómez, Michael S. Inkpen
Language: English
Subfield: Electrical and Electronic Engineering
Field: Engineering
Domain: Physical Sciences
Open Access status: hybrid
Estimated APC paid: $4,500
Awards: Collaborative Research: Acquisition of a 400 MHz NMR at the University of Southern California, G1106303309, G2040979545, G2179135686, G3306068231, G3634295717, G4040018596, MRI: Acquisition of a 600 Mhz NMR Spectrometer at the University of Southern California, G5366184946, G5857724566, Acquisition of a 500 MHz NMR Spectrometer for the University of Southern Calif, G768378720
OpenAlex ID: W4411370565