Constructing single‐molecule parallel circuits with multiple conduction channels is an effective strategy to improve the conductance of a single molecular junction, but rarely reported. We present a novel through‐space conjugated single‐molecule parallel circuit (f‐4Ph‐4SMe) comprised of a pair of closely parallelly aligned p‐quaterphenyl chains tethered by a vinyl bridge and end‐capped with four SMe anchoring groups. Scanning‐tunneling‐microscopy‐based break junction (STM‐BJ) and transmission calculations demonstrate that f‐4Ph‐4SMe holds multiple conductance states owing to different contact configurations. When four SMe groups are in contact with two electrodes at the same time, the through‐bond and through‐space conduction channels work synergistically, resulting in a conductance much larger than those of analogous molecules with two SMe groups or the sum of two p‐quaterphenyl chains. The system is an ideal model for understanding electron transport through parallel π‐stacked molecular systems and may serve as a key component for integrated molecular circuits with controllable conductance.

The single molecular conductance of amino acids was measured by a scanning tunneling microscope (STM) break junction. Conductance measurement of alanine gives out two conductance values at 10−1.85 G0 (1095 nS) and 10−3.7 G0 (15.5 nS), while similar conductance values are also observed for aspartic acid and glutamic acid, which have one more carboxylic acid group compared with alanine. This may show that the backbone of NH2–C–COOH is the primary means of electron transport in the molecular junction of aspartic acid and glutamic acid. However, NH2–C–COOH is not the primary means of electron transport in the methionine junction, which may be caused by the strong interaction of the Au–SMe (methyl sulfide) bond for the methionine junction. The current work reveals the important role of the anchoring group in the electron transport in different amino acids junctions.

In this article, we have investigated the influence of the nitro side-group on the single molecular conductance of pyridine-based molecules by scanning tunneling microscopy break junction. Single molecular conductance of 4,4′-bipyridine (BPY), 3-nitro-4-(pyridin-4-yl)pyridine (BPY-N), and 3-nitro-4-(3-nitropyridin-4-yl)pyridine (BPY-2N) were measured by contact with Au electrodes. For the BPY molecular junction, two sets of conductance were found with values around 10−3.1 G0 (high G) and 10−3.7 G0 (low G). The addition of nitro side-group(s) onto the pyridine ring resulted in lower conductance of 10−3.8 G0 for BPY-N and 10−3.9 G0 for BPY-2N, respectively, which can be attributed to the twist angle of two pyridine rings. Moreover, the steric hindrance of nitro group(s) also affects the contacting configuration of electrode-molecule-electrode. As a consequence, only one set of conductance value was observed for BPY-N and BPY-2N. Our work clearly shows the important role of side-groups on the electron transport of single-molecule junctions.

Tuning of molecular conductance in a liquid environment is a hot topic in molecular electronics. In this article, we explore a new concept where the Fermi level positions of the metallic ends are varied simply by modifying the electroactive salt concentration in solution. We rely on the electrochemical scanning tunneling microscope break junction method that allows the construction in solution of copper atomic contacts that can be then bridged by single molecules. The experimental conductance evolution is first confronted with an analytical formulation that allows the deduction of the molecule's LUMO position and electronic coupling factors. These parameters are in close agreement with those obtained by independent DFT calculations.