Together with the more intuitive and commonly recognized conductance mechanisms of charge‐hopping and tunneling, quantum‐interference (QI) phenomena have been identified as important factors affecting charge transport through molecules. Consequently, establishing simple and flexible molecular‐design strategies to understand, control, and exploit QI in molecular junctions poses an exciting challenge. Here we demonstrate that destructive quantum interference (DQI) in meta‐substituted phenylene ethylene‐type oligomers (m‐OPE) can be tuned by changing the position and conformation of methoxy (OMe) substituents at the central phenylene ring. These substituents play the role of molecular‐scale taps, which can be switched on or off to control the current flow through a molecule. Our experimental results conclusively verify recently postulated magic‐ratio and orbital‐product rules, and highlight a novel chemical design strategy for tuning and gating DQI features to create single‐molecule devices with desirable electronic functions.

High electrical conductance molecular nanowires are highly desirable components for future molecular-scale circuitry, but typically molecular wires act as tunnel barriers and their conductance decays exponentially with length. Here, we demonstrate that the conductance of fused-oligo-porphyrin nanowires can be either length independent or increase with length at room temperature. We show that this negative attenuation is an intrinsic property of fused-oligo-porphyrin nanowires, but its manifestation depends on the electrode material or anchor groups. This highly desirable, nonclassical behavior signals the quantum nature of transport through such wires. It arises because with increasing length the tendency for electrical conductance to decay is compensated by a decrease in their highest occupied molecular orbital-lowest unoccupied molecular orbital gap. Our study reveals the potential of these molecular wires as interconnects in future molecular-scale circuitry.

Single-molecule junctions that are sensitive to compression or elongation are an emerging class of nanoelectromechanical systems (NEMS). Although the moleculeelectrode interface can be engineered to impart such functionality,m ost studies to date rely on poorly defined interactions. We focused on this issue by synthesizing molecular wires designed to have chemically defined hemilabile contacts based on (methylthio)thiophene moieties.W em easured their conductance as af unction of junction sizea nd observed conductance changes of up to two orders of magnitude as junctions were compressed and stretched.Localised interactions between weakly coordinating thienyl sulfurs and the electrodes are responsible for the observed effect and allowr eversible monodentateQbidentate contact transitions as the junction is modulated in size.W eobserved an up to % 100-fold sensitivity boost of the (methylthio)thiophene-terminated molecular wire compared with its non-hemilabile (methylthio)benzene counterpart and demonstrate ap reviously unexplored application of hemilabile ligands to molecular electronics.

Together with the more intuitive and commonly recognized conductance mechanisms of charge‐hopping and tunneling, quantum‐interference (QI) phenomena have been identified as important factors affecting charge transport through molecules. Consequently, establishing simple and flexible molecular‐design strategies to understand, control, and exploit QI in molecular junctions poses an exciting challenge. Here we demonstrate that destructive quantum interference (DQI) in meta‐substituted phenylene ethylene‐type oligomers (m‐OPE) can be tuned by changing the position and conformation of methoxy (OMe) substituents at the central phenylene ring. These substituents play the role of molecular‐scale taps, which can be switched on or off to control the current flow through a molecule. Our experimental results conclusively verify recently postulated magic‐ratio and orbital‐product rules, and highlight a novel chemical design strategy for tuning and gating DQI features to create single‐molecule devices with desirable electronic functions.

We use a scanning tunneling microscope to form and electrically interrogate metal - molecule - metal junctions. To form such junctions, molecules must be functionalised with suitable contact groups (e.g. thiols, thioethers, 4-pyridyls, amines) at each extremity. We show here that 2-(methylthio)thiophene units not only act as contact groups, but can reversibly switch between a monodentate configuration (MeS-only) and a bidentate configuration (MeS- and thienyl S) upon junction compression; as the junction is compressed the electrical conductance increases greatly with the increased molecule-contact interaction. This means that such molecules show a large-amplitude mechanical switching behavior; we also show that this is reversible and that switching can occur at a rate of at least 10 kHz. Control molecules with MeSC6H5 contact groups do not show this behavior. This, together with detailed theoretical and transport calculations on the compressed and extended molecular junctions, supports our contention that it is the thienyl S that is involved in the switching mechanism. <br>