TY - JOUR

T1 - Exploring the impact of select anchor groups for norbornadiene/quadricyclane single-molecule switches

AU - Ghasemi, Shima

AU - Ornago, Luca

AU - Liasi, Zacharias

AU - Johansen, Magnus Bukhave

AU - Von Buchwald, Theo Juncker

AU - Hillers-bendtsen, Andreas Erbs

AU - Van Der Poel, Sebastiaan

AU - Hölzel, Helen

AU - Wang, Zhihang

AU - Amombo Noa, Francoise M.

AU - Öhrström, Lars

AU - Mikkelsen, Kurt V.

AU - Van Der Zant, Herre S. J.

AU - Lara-avila, Samuel

AU - Moth-poulsen, Kasper

PY - 2023

Y1 - 2023

N2 - To achieve the ultimate limit of device miniaturization, it is necessary to have a comprehensive understanding of the structure–property relationship in functional molecular systems used in single-molecule electronics. This study reports the synthesis and characterization of a novel series of norbornadiene derivatives capped with thioether and thioester anchor groups. Utilizing the mechanically controllable break junction technique, the impact of these capping groups on conductance across single-molecule junctions is investigated. Among the selection of anchor groups, norbornadiene capped with thioacetate and tert-butyl groups exhibits higher conductance (G ≈ 4 × 10−4 G0) compared to methyl thioether (G ≈ 2 × 10−4 G0). Electronic transmission through the considered set of single-molecule junctions has been simulated. The computational results for electron transport across these junctions align closely with the experimental findings, with the thioacetate- and tert-butyl-substituted systems outperforming the methyl thioether-capped derivative. In terms of junction stability, the methyl thioether-capped system is the most resilient, maintaining consistent conductance even after approximately 10 000 cycles. Meanwhile, the likelihood of observing molecular plateaus in both the thioacetate- and tert-butyl-substituted systems declines over time. These findings substantially advance both the design and understanding of functional molecular systems in the realm of single-molecule electronics, particularly in the context of molecular photoswitches.

AB - To achieve the ultimate limit of device miniaturization, it is necessary to have a comprehensive understanding of the structure–property relationship in functional molecular systems used in single-molecule electronics. This study reports the synthesis and characterization of a novel series of norbornadiene derivatives capped with thioether and thioester anchor groups. Utilizing the mechanically controllable break junction technique, the impact of these capping groups on conductance across single-molecule junctions is investigated. Among the selection of anchor groups, norbornadiene capped with thioacetate and tert-butyl groups exhibits higher conductance (G ≈ 4 × 10−4 G0) compared to methyl thioether (G ≈ 2 × 10−4 G0). Electronic transmission through the considered set of single-molecule junctions has been simulated. The computational results for electron transport across these junctions align closely with the experimental findings, with the thioacetate- and tert-butyl-substituted systems outperforming the methyl thioether-capped derivative. In terms of junction stability, the methyl thioether-capped system is the most resilient, maintaining consistent conductance even after approximately 10 000 cycles. Meanwhile, the likelihood of observing molecular plateaus in both the thioacetate- and tert-butyl-substituted systems declines over time. These findings substantially advance both the design and understanding of functional molecular systems in the realm of single-molecule electronics, particularly in the context of molecular photoswitches.

U2 - 10.1039/D3TC02652C

DO - 10.1039/D3TC02652C

M3 - Journal article

VL - 11

SP - 15412

EP - 15418

JO - Journal of Materials Chemistry C

JF - Journal of Materials Chemistry C

SN - 2050-7526

IS - 44

ER -