Single-molecule Conductance Research Articles

Design Considerations for Oligo(p-phenyleneethynylene) Organic Radicals in Molecular Junctions

Spin polarization in the electron transmission of radicals is important for understanding single-molecule conductance experiments focusing on shot noise, Kondo properties, or magnetoresistance. We ...

Enhanced Gating Performance of Single-Molecule Conductance by Heterocyclic Molecules.

Enhancing the gating performance of single-molecule conductance is significant for realizing molecular transistors. Herein, we report a new strategy to improve the electrochemical gating efficiency of single-molecule conductance with fused molecular structures consisting of heterocyclic rings of furan, thiophene, or selenophene. One order magnitude of gating ratio is achieved within a potential window of 1.2 V for the selenophene-based molecule, which is significantly greater than that of other heterocyclic and benzene ring molecules. This is caused by the different electronic structures of heterocyclic molecules and transmission coefficients T(E), and preliminary resonance tunneling is achieved through the highest occupied molecular orbital at high potential. The current work experimentally shows that electrochemical gating performance can be significantly modulated by the alignment of the conducting orbital of the heterocyclic molecule relative to the metal Fermi energy.

Modulation of destructive quantum interference by bridge groups in truxene-based single-molecule junctions.

Electron transport properties of polycyclic truxene derivatives have been investigated by the single molecule conductance measurement technique and theoretical study. Molecules with nitrogen and carbonyl substituents at the bridge sites exhibit higher single-molecule conductances by almost one order of magnitude compared with non-substituted analogues. It can be ascribed that the anti-resonance feature produced by destructive quantum interference (DQI) is alleviated and pushed away from the Fermi energy. These findings provide an effective chemical strategy for manipulating the DQI behavior in single molecular devices.

Experimental Validation of Quantum Circuit Rules in Molecular Junctions

A series of diarylacetylene (tolane) derivatives functionalised at the 4- and 4′-positions by thiolate, thioether, or amine groups capable of serving as anchor groups to secure the molecules within a molecular junction have been prepared and characterised. The series of compounds have a general form X-B-X, Y-B-Y, and X-B-Y where X and Y represent anchor groups and B the molecular bridge. The single-molecule conductance values determined by the scanning tunnelling microscope break-junction method are found to be in excellent agreement with the predictions made on the basis of a recently proposed ‘molecular circuit law’, which states ‘the conductance CH21136_IE1.gif of an asymmetric molecule X-B-Y is the geometric mean CH21136_IE2.gif of the conductance of the two symmetric molecules derived from it, CH21136_IE3.gif and CH21136_IE4.gif.’ The experimental verification of the circuit law, which holds for systems in which the constituent moieties X, B, and Y are weakly coupled and whose conductance takes place via off-resonance tunnelling, gives further confidence in the use of this relationship in the design of future compounds for use in molecular electronics research.

Synthesis and molecular properties of isomeric thienoisoindigo

The luminescence and single-molecule conductance of the lactam molecules can be effectively regulated by changing the ring-fusion mode and the amide arrangement of lactam units.

Three-state molecular potentiometer based on a non-symmetrically positioned in-backbone linker

We report on the synthesis and single-molecule conductance of a para-oligo(phenylene)ethynylene derivative with a non-symmetric positioned internal anchor group that gives rise to three conduction pathways of well distinctive conductance and length.

Single-molecule conductance variations of up to four orders of magnitude via contacting electrodes with different anchoring sites

Control of conductance through a single molecule via alternating anchoring points provides a unique perspective to design single-molecule electronic devices.

Promotion and Suppression of Single-Molecule Conductance by Quantum Interference in Macrocyclic Circuits

In order to rival the performance of silicon-integrated systems, molecular-scale circuits must be designed to enable the construction of different electronic components. A common strategy is to manipulate the quantum interference (QI) between frontier orbitals close to the electrode Fermi energy. Aligning the energies of these molecular orbitals, however, remains a formidable challenge. Herein, we demonstrate a modular design of single-molecule circuits, which enable the construction of basic electronic components — namely, conductors or insulators — based on one tetracationic cyclophane platform. We demonstrate that the electron transport in cyclophane circuits is mediated by QI between channels formed from two lowest unoccupied molecular orbitals (LUMOs), while their highest occupied molecular orbitals (HOMOs) play no significant role. We further reveal that energy differences between these two LUMO channels induce constructive interference, leading to high conductance. By contrast, the phase differences between these LUMO channels result in destructive interference and a suppression in the overall conductance.

Single-molecule determination of chemical equilibrium of DNA intercalation by electrical conductance.

We investigated a single-molecule reaction of DNA intercalation as an example of a bimolecular association reaction. Single-molecule conductance values of the product and reactant molecules adsorbed on an Au surface were measured to identify and quantify these molecules. The binding isotherm was constructed, and the association constant of the reaction was determined on a single-molecule basis.

Improving Intramolecular Hopping Charge Transport via Periodical Segmentation of π-Conjugation in a Molecule.

The development of several-nanometer-scale π-conjugated systems for efficient intramolecular hopping charge transport remains a significant challenge. To construct localized electronic structures at the same energy in a molecule, a series of oligothiophenes, with lengths up to 10 nm and periodically twisted structures, was synthesized. Single-molecule conductance measurements of the twisted molecules revealed resistances lower than those of planar oligothiophenes. This study provides a rational molecular design to improve the intramolecular hopping charge transport in materials.

Single-Molecule Conductance of a π-Hybridized Tripodal Anchor while Maintaining Electronic Communication.

Direct hybridization between the π-orbital of a conjugated molecule and metal electrodes is recognized as a new anchoring strategy to enhance the electrical conductance of single-molecule junctions. The anchor is expected to maintain direct hybridization between the conjugated molecule and the metal electrodes, and control the orientation of the molecule against the metal electrodes. However, fulfilling both requirements is difficult because multipodal anchors aiming at a robust contact with the electrodes often break the π-conjugation, thereby resulting in an inefficient carrier transport. Herein, a new tripodal anchor framework-a 7,7-diphenyl-7H-benzo[6,7]indeno[1,2-b]thiophene (PBIT) derivative-is developed. In this framework, π-conjugation is maintained in the molecular junction, and the tripodal structure makes the molecule stand upright on the metal electrode. Molecular conductance is measured by the break junction technique. A vector-based classification and first-principles transport calculations determine the single-molecule conductance of the tripodal-anchoring structure. The conductance of the PBIT-based molecule is higher than that of the tripodal anchor having sp3 carbon atoms in the carrier transport pathway. These results demonstrate that extending the π-conjugation to the tripodal leg is an effective strategy for enhancing the conductivities of single-molecule junctions.

Electrochemistry of complex molecular and biomolecular scale entities

Structural mapping of intermediate size and large molecules and biomolecules at ultra-high resolution using single-crystal electrodes and in situ scanning tunnelling microscopy continues to disclose surprising findings. In situ scanning tunnelling spectroscopy has also recently disclosed new electrochemical conductivity features at the level of the single molecule. We overview briefly elements of this development over the last few years, with focus on three recent discoveries: (1) a new packing mode of a core monolayer target thiol, the amino acid cysteine (Cys) on Au(100)-electrodes, quite different from Cys packing on Au(111)- and Au(110)-electrodes; (2) transition of a core ferrocene in situ scanning tunnelling spectroscopy probe from stochastic single-molecule to macroscopic behaviour, a concept at the heart of nanoscience; and (3) unexpected behaviour of the large molybdenum enzyme sulfite oxidase, when going from macroscopic to single-molecule electrochemistry. We compare these studies with other recent discoveries of single-molecule protein conductivity and molecular scale inorganic nanostructures.

Determination of Ag[I] and NADH Using Single-Molecule Conductance Ratiometric Probes.

The sensing platform based on single-molecule measurements provides a new perspective for constructing ultrasensitive systems. However, most of these sensing platforms are unavailable for the accurate determination of target analytes. Herein, we demonstrate a conductance ratiometric strategy combing with the single-molecule conductance techniques for ultrasensitive and precise determination. A single-molecule sensing platform was constructed with the 3,3',5,5'-tetramethylbenzidine (TMB) and oxidized TMB (oxTMB) as the conductance ratiometric probes, which was applied in the detection of Ag[I] and nicotinamide adenine dinucleotide (NADH). It was found that the charge transport properties of TMB and oxTMB were distinct with more than an order of magnitude change of the conductance, thus enabling conductance ratiometric analysis of the Ag[I] and NADH in the real samples. The proposed method is ultrasensitive and has an anti-interference ability in the complicated matrix. The limit of detection can be as low as attomolar concentrations (∼34 aM). We believe that the proposed conductance ratiometric approach is generally enough to have a promising potential for broad and complicated analysis.

Length Discrimination of Homo-oligomeric Nucleic Acids with Single-molecule Measurement.

Single-molecule DNA/RNA sequencing based on single-molecule measurement is a prominent method for higher throughput sequencing. In a previous report, the single-molecule DNA/RNA sequencing method has applied to detect each base-conductance difference in the tunneling current time profiles, and determined the sequence. However, discrimination of identical base lengths has not yet been achieved. The number of the identical contiguous bases has importance in biology because some homopolymers of nucleic acid control gene expression. In this study, we aimed to develop a method for discriminating the length of homopolymer of nucleic acids of adenosine monophosphate (AMP) using a single-molecule sequencing technique. We carried out single-molecule conductance measurements of adenine pentamer, hexamer and heptamer. The single-molecule signals of the oligomers are not distinguishable from current and duration time histograms. The three oligomers were discriminated by our developed machine learning-based analysis with accuracy of 0.54 for a single signal, and 99% for 40 signals. This method will be applied to the single signals and identify the contiguous bases in the sequence and provide new biological insights.

Cumulene Wires Display Increasing Conductance with Increasing Length.

One-dimensional sp-hybridized carbon wires, including cumulenes and polyynes, can be regarded as finite versions of carbynes. They are likely to be good candidates for molecular-scale conducting wires as they are predicted to have a high-conductance. In this study, we first characterize the single-molecule conductance of a series of cumulenes and polyynes with a backbone ranging in length from 4 to 8 carbon atoms, including [7]cumulene, the longest cumulenic carbon wire studied to date for molecular electronics. We observe different length dependence of conductance when comparing these two forms of carbon wires. Polyynes exhibit conductance decays with increasing molecular length, while cumulenes show a conductance increase with increasing molecular length. Their distinct conducting behaviors are attributed to their different bond length alternation, which is supported by theoretical calculations. This study confirms the long-standing theoretical predictions on sp-hybridized carbon wires and demonstrates that cumulenes can form highly conducting molecular wires.

Intermolecular Effects on Tunneling through Acenes in Large-Area and Single-Molecule Junctions

This paper describes the conductance of single-molecules and self-assembled monolayers comprising an oligophenyleneethynylene core, functionalized with acenes of increasing length that extend conjugation perpendicular to the path of tunneling electrons. In the Mechanically Controlled Break Junction (MCBJ) experiment, multiple conductance plateaus were identified. The high conductance plateau, which we attribute to the single molecule conformation, shows an increase of conductance as a function of acene length, in good agreement with theoretical predictions. The lower plateau is attributed to multiple molecules bridging the junctions with intermolecular interactions playing a role. In junctions comprising a self-assembled monolayer with eutectic Ga–In top-contacts (EGaIn), the pentacene derivative exhibits unusually low conductance, which we ascribe to the inability of these molecules to pack in a monolayer without introducing significant intermolecular contacts. This hypothesis is supported by the MCBJ data and theoretical calculations showing suppressed conductance through the PC films. These results highlight the role of intermolecular effects and junction geometries in the observed fluctuations of conductance values between single-molecule and ensemble junctions, and the importance of studying molecules in both platforms.

The conductance of conformers

Single-molecule conductance measurements enable different conformers of cyclohexane to be observed at room temperature.

Switching Quantum Interference in Phenoxyquinone Single Molecule Junction with Light.

Quantum interference (QI) can lead to large variations in single molecule conductance. However, controlling QI using external stimuli is challenging. The molecular structure of phenoxyquinone can be tuned reversibly using light stimulus. In this paper, we show that this can be utilized to control QI in phenoxyquinone derivatives. Our calculations indicate that, as a result of such variation in molecular structure of phenoxyquinone, a crossover from destructive to constructive QI is induced. This leads to a significant variation in the single molecule conductance by a couple of orders of magnitude. This control of QI using light is a new paradigm in photosensitive single molecule switches and opens new avenues for future QI-based photoswitches.

Single-Molecule Junction of a Cationic Rh(III) Polyyne Molecular Wire.

Single-molecule conductance studies on metal-containing inorganic and organometallic molecular wires are relatively less explored compared to those on organic molecular wires. Furthermore, conductance and transmission profiles of the metal-containing wires insensitive to the metal centers often hinder rational design for high performance wires. Here, synthesis and single-molecule conductance measurements of the bis(butadiynyl)rhodium wires with tetracarbene ligands 1H and 1Au are reported as rare examples for Rh(III) diacetylide molecular wires. The rhodium wires derived from the terminal acetylene and gold-functionalized precursors show comparable, high single-molecule conductance ((6-7) × 10-3 G0) as determined by the STM break-junction measurements, suggesting formation of virtually the same covalently linked metal electrode-molecule-metal electrode junctions. The values for the metallapolyynes are larger than those of the organic polyyne wires having the similar molecular lengths. The hybrid DFT-NEGF calculations of the model systems suggest that profiles of transmission spectra are highly sensitive to the presence and species of the metal fragments doped into the polyyne molecular wire because the conductance orbitals of the metallapolyynes molecular junctions carry significant metal fragment characters. Thus, the metallapolyyne junctions turn out to be suitable platforms for rationally designed molecular wires.

Mechanically Tunable Quantum Interference in Ferrocene-Based Single-Molecule Junctions.

Ferrocenes are ubiquitous organometallic building blocks that comprise a Fe atom sandwiched between two cyclopentadienyl (Cp) rings that rotate freely at room temperature. Of widespread interest in fundamental studies and real-world applications, they have also attracted some interest as functional elements of molecular-scale devices. Here we investigate the impact of the configurational degrees of freedom of a ferrocene derivative on its single-molecule junction conductance. Measurements indicate that the conductance of the ferrocene derivative, which is suppressed by 2 orders of magnitude as compared to a fully conjugated analogue, can be modulated by altering the junction configuration. Ab initio transport calculations show that the low conductance is a consequence of destructive quantum interference effects of the Fano type that arise from the hybridization of localized metal-based d-orbitals and the delocalized ligand-based π-system. By rotation of the Cp rings, the hybridization, and thus the quantum interference, can be mechanically controlled, resulting in a conductance modulation that is seen experimentally.