Controlling the electrical conductance and in particular the occurrence of quantum interference in single-molecule junctions through gating effects, has potential for the realization of highperformance functional molecular devices. In this work, we used an electrochemically-gated, mechanically-controllable break junction technique to tune the electronic behaviour of thiophene-based molecular junctions that show destructive quantum interference (DQI) features. By varying the voltage applied to the electrochemical gate at room temperature, we

Organic thermoelectric materials have potential for wearable heating, cooling, and energy generation devices at room temperature. For this to be technologically viable, high-conductance (G) and high-Seebeck-coefficient (S) materials are needed. For most semiconductors, the increase in S is accompanied by a decrease in G. Here, using a combined experimental and theoretical investigation, we demonstrate that a simultaneous enhancement of S and G can be achieved in single organic radical molecules, thanks to their intrinsic spin state. A counterintuitive quantum interference (QI) effect is also observed in stable Blatter radical molecules, where constructive QI occurs for a meta-connected radical, leading to further enhancement of thermoelectric properties. Compared to an analogous closed-shell molecule, the power factor is enhanced by more than 1 order of magnitude in radicals. These results open a new avenue for the development of organic thermoelectric materials operating at room temperature.

Controlling charge transport through molecules is challenging because it requires engineering of the energy of molecular orbitals involved in the transport process. While side groups are central to maintaining solubility in many molecular materials, their role in modulating charge transport through single-molecule junctions has received less attention. Here, using two break-junction techniques and computational modeling, we investigate systematically the effect of electron-donating and -withdrawing side groups on the charge transport through single molecules. By characterizing the conductance and thermopower, we demonstrate that side groups can be used to manipulate energy levels of the transport orbitals. Furthermore, we develop a novel statistical approach to model quantum transport through molecular junctions. The proposed method does not treat the electrodes’ chemical potential as a free parameter and leads to more robust prediction of electrical conductance as confirmed by our experiment. The new method is generic and can be used to predict the conductance of molecules.

Atomically precise graphene nanoribbons (GNRs) are increasingly attracting interest due to their largely modifiable electronic properties, which can be tailored by controlling their width and edge structure during chemical synthesis. In recent years, the exploitation of GNR properties for electronic devices has focused on GNR integration into field‐effect‐transistor (FET) geometries. However, such FET devices have limited electrostatic tunability due to the presence of a single gate. Here, on the device integration of 9‐atom wide armchair graphene nanoribbons (9‐AGNRs) into a multi‐gate FET geometry, consisting of an ultra‐narrow finger gate and two side gates is reported. High‐resolution electron‐beam lithography (EBL) is used for defining finger gates as narrow as 12 nm and combine them with graphene electrodes for contacting the GNRs. Low‐temperature transport spectroscopy measurements reveal quantum dot (QD) behavior with rich Coulomb diamond patterns, suggesting that the GNRs form QDs that are connected both in series and in parallel. Moreover, it is shown that the additional gates enable differential tuning of the QDs in the nanojunction, providing the first step toward multi‐gate control of GNR‐based multi‐dot systems.

Indium tin oxide (ITO) is an attractive substrate for single-molecule electronics since it is transparent while maintaining electrical conductivity. Although it has been used before as a contacting electrode in single-molecule electrical studies, these studies have been limited to the use of carboxylic acid terminal groups for binding molecular wires to the ITO substrates. There is thus the need to investigate other anchoring groups with potential for binding effectively to ITO. With this aim, we have investigated the single-molecule conductance of a series of eight tolane or “tolane-like” molecular wires with a variety of surface binding groups. We first used gold–molecule–gold junctions to identify promising targets for ITO selectivity. We then assessed the propensity and selectivity of carboxylic acid, cyanoacrylic acid, and pyridinium-squarate to bind to ITO and promote the formation of molecular heterojunctions. We found that pyridinium squarate zwitterions display excellent selectivity for binding to ITO over gold surfaces, with contact resistivity comparable to that of carboxylic acids. These single-molecule experiments are complemented by surface chemical characterization with X-ray photoelectron spectroscopy, quartz crystal microbalance, contact angle determination, and nanolithography using an atomic force miscroscope. Finally, we report the first density-functional theory calculations involving ITO electrodes to model charge transport through ITO–molecule–gold heterojunctions.

Graphene nanoribbons synthesized using bottom-up approaches can be structured with atomic precision, allowing their physical properties to be precisely controlled. For applications in quantum technology, the manipulation of single charges, spins or photons is required. However, achieving this at the level of single graphene nanoribbons is experimentally challenging due to the difficulty of contacting individual nanoribbons, particularly on-surface synthesized ones. Here we report the contacting and electrical characterization of on-surface synthesized graphene nanoribbons in a multigate device architecture using single-walled carbon nanotubes as the electrodes. The approach relies on the self-aligned nature of both nanotubes, which have diameters as small as 1 nm, and the nanoribbon growth on their respective growth substrates. The resulting nanoribbon–nanotube devices exhibit quantum transport phenomena—including Coulomb blockade, excited states of vibrational origin and Franck–Condon blockade—that indicate the contacting of individual graphene nanoribbons.

Most studies in molecular electronics focus on altering the molecular wire backbone to tune the electrical properties of the whole junction. However, it is often overlooked that the chemical structure of the groups anchoring the molecule to the metallic electrodes influences the electronic structure of the whole system and, therefore, its conductance. We synthesised electron-accepting dithienophosphole oxide derivatives and fabricated their singlemolecule junctions. We found that the anchor group has a dramatic effect on charge-transport efficiency: in our case, electron-deficient 4-pyridyl contacts suppress conductance, while electron-rich 4-thioanisole termini promote efficient transport. Our calculations show that this is due to minute changes in charge distribution, probed at the electrode interface. Our findings provide a framework for efficient molecular junction design, especially valuable for compounds with strong electron withdrawing/donating backbones.

Controlling charge transport through molecular wires by utilizing quantum interference (QI) is a growing topic in single-molecular electronics. In this article, scanning tunneling microscopy-break junction techniques and density functional theory calculations are employed to investigate the single-molecule conductance properties of four molecules that have been specifically designed to test extended curly arrow rules (ECARs) for predicting QI in molecular junctions. Specifically, for two new isomeric 1-phenylpyrrole derivatives, the conductance pathway between the gold electrodes must pass through a nitrogen atom: this novel feature is designed to maximize the influence of the heteroatom on conductance properties and has not been the subject of prior investigations of QI. It is shown, experimentally and computationally, that the presence of a nitrogen atom in the conductance pathway increases the effect of changing the position of the anchoring group on the phenyl ring from para to meta , in comparison with biphenyl analogues. This effect is explained in terms of destructive QI (DQI) for the meta -connected pyrrole and shifted DQI for the para -connected isomer. These results demonstrate modulation of antiresonances by molecular design and verify the validity of ECARs as a simple “pen-and-paper” method for predicting QI behavior. The principles offer new fundamental insights into structure–property relationships in molecular junctions and can now be exploited in a range of different heterocycles for molecular electronic applications, such as switches based on external gating, or in thermoelectric devices.