Single-molecule Junctions Research Articles

Destructive quantum interference in meta-oligo(phenyleneethynylene) molecular wires with gold-graphene heterojunctions.

Quantum interference (QI) is well recognised as a significant contributing factor to the magnitude of molecular conductance values in both single-molecule and large area junctions. Numerous structure-property relationship studies have shown that para-connected oligo(phenyleneethynylene) (OPE) based molecular wires exemplify the impact of constructive quantum interference (CQI), whilst destructive quantum interference (DQI) effects are responsible for the orders of magnitude lower conductance of analogous meta-contacted OPE derivatives, despite the somewhat shorter effective tunnelling distance. Since molecular conductance is related to the value of the transmission function, evaluated at the electrode Fermi energy, T(EF), which in turn is influenced by the presence and relative energy of (anti)resonances, it follows that the relative single-molecule conductance of para- and meta-contacted OPE-type molecules is tuned both by the anchor group and the nature of the electrode materials used in the construction of molecular junctions (gold|molecule|gold vs. gold|molecule|graphene). It is shown here that whilst amine-contacted junctions show little influence of the electrode material on molecular conductance due to the similar electrode-molecule coupling through this anchor group to both types of electrodes, the weaker coupling between thiomethyl and ethynyl anchors and the graphene substrate electrode results in a relative enhancement of the DQI effect. This work highlights an additional parameter space to explore QI effects and establishes a new working model based on the electrode materials and anchor groups in modulating QI effects beyond the chemical structure of the molecular backbone.

Phenol is a pH-activated linker to gold: a single molecule conductance study.

Single molecule conductance measurements typically rely on functional linker groups to anchor the molecule to the conductive electrodes through a donor-acceptor or covalent bond. While many linking moieties, such as thiols, amines, thiothers and phosphines have been used among others, very few involve oxygen binding directly to gold electrodes. Here, we report successful single molecule conductance measurements using hydroxy (OH)-containing phenol linkers and show that the molecule-gold attachment and electron transport are mediated by a direct O-Au bond. We find that deprotonation of the hydroxy moiety is necessary for metal-molecule binding to proceed, so that junction formation can be activated through pH control. Electronic structure and DFT+Σ transport calculations confirm our experimental findings that phenolate-terminated alkanes can anchor on the gold and show charge transport trends consistent with prior observations of alkane conductance with other linker groups. Critically, the deprotonated O--Au binding shows features similar to the thiolate-Au bond, but without the junction disruption caused by intercalation of sulfur into electrode tips often observed with thiol-terminated molecules. By comparing the conductance and binding features of O-Au and S-Au bonds, this study provides insight into the aspects of Au-linker bonding that promote reproducible and robust single molecule junction measurements.

Robust binding between secondary amines and Au electrodes.

While primary amines are one of the most widely used linker groups for forming single-molecule junctions, it remains elusive whether and how the substitution of one hydrogen in a primary amine with a methyl group (secondary amine) can alter its functional properties as a linker group. Here we show that a robust binding between a secondary amine and an Au electrode is absent with the use of a non-coated Au tip and is achieved when in contact with a wax-coated Au tip, which we propose is catalyzed by the more frequent formation of Au adatoms in measurements with a wax-coated tip.

Reliable I/V characteristics and long lifetime of porphyrin-based single-molecule junctions

In this work diamino-porphyrin derivatives, in their free base or cobalt complex forms, have been used to construct SMJs.

Theoretical and modelling investigation of pendant groups effect on quantum interference for single-molecule junctions.

Quantum interference (QI) is one of the most important phenomena that affects the charge transport through single molecules. The effect of a constructive and destructive quantum interference on electronic, thermoelectric and spectroscopic properties of oligo(phenyleneethynylene) based-molecular junctions has been investigated using a combination of density functional theory (DFT) methods, tight binding (Hückel) modelling (TBHM) and quantum transport theory (QTT). Molecules with carbonyl, diphenyl, ethane and ethynylferrocene substituents show a destructive quantum interference (DQI), which enhances thermoelectric properties of these molecules making them promising materials for thermoelectric applications.

The regulation effect of coordination number on the conductance of single-molecule junctions

The molecules with multiple anchoring sites offer opportunities for conductance regulation of single-molecule junctions via a switch between different coordination numbers.

Thermoelectric Signature of d-orbitals in Tripod-Based Molecular Junctions

Thermoelectric properties of single-molecule junctions is a significant goal of a wide range of studies. Herein, the excellent consistent between the current theoretical results and experimental outcomes of previous studies...

A new anchoring group to fabricate single-molecule junctions: diphenyl sulfide

A new anchor (–SPh) was confirmed with the ability to enable reproducible molecular junction formation.

Significant thermal rectification induced by phonon mismatch of functional groups in a single-molecule junction

Single-molecule junctions (SMJs) may bring exotic physical effects. In this work, a significant thermal rectification effect is observed in a cross-dimensional system, comprising a diamond, a single-molecule junction, and a carbon nanotube (CNT). The molecular dynamics simulations indicate that the interfacial thermal resistance varies with the direction of heat flow, the orientation of the crystal planes of the diamond, and the length of the CNT. We find that the thermal rectification ratio escalates with the length of the CNT, achieving a peak value of 730% with the CNT length of 200 nm. A detailed analysis of phonon vibrations suggests that the primary cause of thermal rectification is the mismatched vibrations between the biphenyl and carbonyl groups. This discovery may offer theoretical insights for both the experimental exploration and practical application of SMJs in efficient thermal management strategy for high power and highly integrated chips.

Plasmon-Molecule Interactions in Single-Molecule Junctions.

Single-molecule optoelectronics offers opportunities for advancing integrated photonics and electronics, which also serves as a tool to elucidate the underlying mechanism of light-matter interaction. Plasmonics, which plays pivotal role in the interaction of photons and matter, have became an emerging area. A comprehensive understanding of the plasmonic excitation and modulation mechanisms within single-molecule junctions (SMJs) lays the foundation for optoelectronic devices. Consequently, this review primarily concentrates on illuminating the fundamental principles of plasmonics within SMJs, delving into their research methods and modulation factors of plasmon-exciton. Moreover, we underscore the interaction phenomena within SMJs, including the enhancement of molecular fluorescence by plasmonics, Fano resonance and Rabi splitting caused by the interaction of plasmon-exciton. Finally, by emphasizing the potential applications of plasmonics within SMJs, such as their roles in optical tweezers, single-photon sources, super-resolution imaging, and chemical reactions, we elucidate the future prospects and current challenges in this domain.

Metallaaromatic Complexes as Candidates for Future Molecular Materials and Electronic Devices: Recent Advancements.

In recent years, the field of organometallic chemistry has made a great progress and diverse types of metallaaromatics have successively been reported. In those studies, incorporation of ligated osmium centers into metallaaromatic systems played a prominent role. The reviewed literature documents that certain metallaaromatics with unconventional photophysical properties, redox and electronic transport properties and magnetism, have potential to be widely used in diverse practical applications, with selected examples of amino acid and fluoride anion identification, photothermal effects, functional materials, photodynamic therapy (PDT) in biomedicine, single-molecule junction conductors, and electron-transport layer materials (ETLs) in solar cells.

The role of halogens in Au–S bond cleavage for energy-differentiated catalysis at the single-bond limit

The transformation from one compound to another involves the breaking and formation of chemical bonds at the single-bond level, especially during catalytic reactions that are of great significance in broad fields such as energy conversion, environmental science, life science and chemical synthesis. The study of the reaction process at the single-bond limit is the key to understanding the catalytic reaction mechanism and further rationally designing catalysts. Here, we develop a method to monitor the catalytic process from the perspective of the single-bond energy using high-resolution scanning tunneling microscopy single-molecule junctions. Experimental and theoretical studies consistently reveal that the attack of a halogen atom on an Au atom can reduce the breaking energy of Au−S bonds, thereby accelerating the bond cleavage reaction and shortening the plateau length during the single-molecule junction breaking. Furthermore, the distinction in catalytic activity between different halogen atoms can be compared as well. This study establishes the intrinsic relationship among the reaction activation energy, the chemical bond breaking energy and the single-molecule junction breaking process, strengthening our mastery of catalytic reactions towards precise chemistry.

Tailoring single-molecule conductance with structured graphene electrodes

Modulation of electric currents through single-molecule junctions is usually achieved by synthesis of molecules with desired functionalities, in conjunction with suitable molecule–electrode contacts through specific anchoring groups. An alternative to this approach, barely explored so far, is to use structured electrodes, where conductivity could eventually be controlled by changing the specific anchoring site within the very same electrode. Here, we theoretically investigate how to exploit the pronounced anisotropy of corrugated graphene deposited on Ru(0001) (Gr/Ru) to tailor single-molecule conductivity in 4-aminophenyl and 4-aminobenzonitrile. We show that currents induced in the upper and lower anchoring positions in the Gr/Ru moiré are substantially different, irrespective of the chosen molecule. The magnitude of these currents can differ by as much as an order of magnitude at specific bias voltages. We also show that both molecules display rectifying properties, which can differ by up to a factor of five in different anchoring sites. Interestingly, the observed modulations strongly depend on the chemical binding nature between the molecule and the electrode, (strong) covalent bond for 4-aminophenyl and (weak) physisorption for 4-aminobenzonitrile. All this suggests that Gr/Ru can be an ideal electrode to modulate single-molecule electric conductivity under experimental conditions that are available in many laboratories.

Resonant Charge Transport Assisted by the Molecular Vibration in Single-Molecule Junction from Time-Domain ab initio Nonadiabatic Molecular Dynamics Simulations

Using ab initio nonadiabatic molecular dynamics simulation, we study the time-dependent charge transport dynamics in a single-molecule junction formed by gold (Au) electrodes and a single benzene-1,4-dithiol (BDT) molecule. Two different types of charge transport channels are found in the simulation. One is the routine non-resonant charge transfer path, which occurs in several picoseconds. The other is activated when the electronic state of the electrodes and that of the molecule get close in energy, which is referred to as the resonant charge transport. More strikingly, the resonant charge transfer occurs in an ultrafast manner within 100 fs, which notably increases the conductance of the device. Further analysis shows that the resonant charge transport is directly assisted by the B 2 and A 1 molecular vibration modes. Our study provides atomic insights into the time-dependent charge transport dynamics in single-molecule junctions, which is important for designing highly efficient single-molecule devices.

Electrical Conductance and Thermopower of β-Substituted Porphyrin Molecular Junctions─Synthesis and Transport.

Molecular junctions offer significant potential for enhancing thermoelectric power generation. Quantum interference effects and associated sharp features in electron transmission are expected to enable the tuning and enhancement of thermoelectric properties in molecular junctions. To systematically explore the effect of quantum interferences, we designed and synthesized two new classes of porphyrins, P1 and P2, with two methylthio anchoring groups in the 2,13- and 2,12-positions, respectively, and their Zn complexes, Zn-P1 and Zn-P2. Past theory suggests that P1 and Zn-P1 feature destructive quantum interference in single-molecule junctions with gold electrodes and may thus show high thermopower, while P2 and Zn-P2 do not. Our detailed experimental single-molecule break-junction studies of conductance and thermopower, the latter being the first ever performed on porphyrin molecular junctions, revealed that the electrical conductance of the P1 and Zn-P1 junctions is relatively close, and the same holds for P2 and Zn-P2, while there is a 6 times reduction in the electrical conductance between P1 and P2 type junctions. Further, we observed that the thermopower of P1 junctions is slightly larger than for P2 junctions, while Zn-P1 junctions show the largest thermopower and Zn-P2 junctions show the lowest. We relate the experimental results to quantum transport theory using first-principles approaches. While the conductance of P1 and Zn-P1 junctions is robustly predicted to be larger than those of P2 and Zn-P2, computed thermopowers depend sensitively on the level of theory and the single-molecule junction geometry. However, the predicted large difference in conductance and thermopower values between Zn-P1 and Zn-P2 derivatives, suggested in previous model calculations, is not supported by our experimental and theoretical findings.

Understanding Current Density in Molecules Using Molecular Orbitals.

While the use of molecular orbitals (MOs) and their isosurfaces to explain physical phenomena in chemical systems is a time-honored tool, we show that the nodes are an equally important component for understanding the current density through single-molecule junctions. We investigate three different model systems consisting of an alkane, alkene, and even [n]cumulene and show that we can explain the form of the current density using the MOs of the molecule. Essentially, the MOs define the region in which current can flow and their gradients define the direction in which current flows within that region. We also show that it is possible to simplify the current density for improved understanding by either partitioning the current density into more chemically intuitive parts, such as σ- and π-systems, or by filtering out MOs with negligible contributions to the overall current density. Our work highlights that it is possible to infer a non-equilibrium property (current density) given only equilibrium properties (MOs and their gradients), and this, in turn, grants deeper insight into coherent electron transport.

Stereoelectronic Switches of Single-Molecule Junctions through Conformation-Modulated Intramolecular Coupling Approaches.

Stereoelectronic effects in single-molecule junctions have been widely utilized to achieve a molecular switch, but high-efficiency and reproducible switching remain challenging. Here, we demonstrate that there are three stable intramolecular conformations in the 9,10-diphenyl-9,10-methanoanthracen-11-one (DPMAO) systems due to steric effect. Interestingly, different electronic coupling approaches including weak coupling (through-space), decoupling, and strong coupling (through-bond) between two terminal benzene rings are accomplished in the three stable conformations, respectively. Theoretical calculations show that the molecular conductance of three stable conformations differs by more than 1 order of magnitude. Furthermore, the populations of the three stable conformations are highly dependent on the solvent effect and the external electric field. Therefore, an excellent molecular switch can be achieved using the DPMAO molecule junctions and external stimuli. Our findings reveal that modulating intramolecular electronic coupling approaches may be a useful manner to enable molecular switches with high switching ratios. This opens up a new route for building high-efficiency molecular switches in single-molecular junctions.

Rational Design of Photocontrolled Rectifier Switches in Single-Molecule Junctions Based on Diarylethene.

The construction of multifunctional, single-molecule nanocircuits to achieve the miniaturization of active electronic devices is a challenging goal in molecular electronics. In this paper, we present an effective strategy for enhancing the multifunctionality and switching performance of diarylethene-based molecular devices, which exhibit photoswitchable rectification properties. Through a molecular engineering design, we systematically investigate a series of electron donor/acceptor-substituted diarylethene molecules to modulate the electronic properties and investigate the transport behaviors of the molecular junctions using the non-equilibrium Green's function combined with the density functional theory. Our results demonstrate that the asymmetric configuration, substituted by both the donor and acceptor on the diarylethene molecule, exhibits the highest switching ratio and rectification ratio. Importantly, this rectification function can be switched on/off through the photoisomerization of the diarylethene unit. These modulations in the transport properties of these molecular junctions with different substituents were obtained with molecule-projected self-consistent Hamiltonian and bias-dependent transmission spectra. Furthermore, the current-voltage characteristics of these molecular junctions can be explained by the molecular energy level structure, showing the significance of energy level regulation. These findings have practical implications for constructing high-performance, multifunctional molecular-integrated circuits.

Mechanism of rectification and negative differential resistance in single-molecule junctions with asymmetric anchoring groups: a DFT study.

This study aims to investigate the electronic transport properties of tetracene molecule connected to gold (Au) electrodes with asymmetric anchoring groups. More specifically, we investigate the effect of asymmetric electrode coupling on the rectification ratio of tetracene-based molecular device. To introduce coupling asymmetry in these junctions, one end of the tetracene molecule is terminated with thiol (-SH) or isocyanide (-NC) while the other end with amine (-NH2) or nitro (-NO2) anchoring group. The results indicate that the electronic transport behavior is affected by the nature of molecule-electrode coupling, and the rectification ratio can be modulated by a proper choice of the anchoring groups. We reveal that the tetracene molecule when connected with isocyanide and amine combination exhibits remarkable rectifying performance (with a rectification ratio of 74) in contrast with other configurations. Furthermore, a prominent negative differential resistance (NDR) feature is observed when the molecule is connected with thiol as one of the anchors. Our present findings with excellent rectifying performance and negative differential resistance pave a new roadmap for designing multifunctional molecular devices. By applying non-equilibrium Green's function (NEGF) formalism combined with density functional theory (DFT) Atomistic Tool Kit software package, the electronic transport properties of tetracene molecule connected to gold electrodes with asymmetric anchoring groups have been investigated. The calculations were performed using the Perdew-Burke-Ernzerhof (PBE) parameterization of DFT within generalized gradient approximation (GGA) exchange-correlation functional. To improve calculation precision and save computational efforts, the molecule and anchor groups were double-ζ (DZ) polarized, while single-ζ (SZ) polarized basis set was used for gold electrodes.

An Orthogonal Conductance Pathway in Spiropyrans for Well-Defined Electrosteric Switching Single-Molecule Junctions.

While a multitude of studies have appeared touting the use of molecules as electronic components, the design of molecular switches is crucial for the next steps in molecular electronics. In this work, single-molecule devices incorporating spiropyrans, made using break junction techniques, are described. Linear spiropyrans with electrode-contacting groups linked by alkynyl spacers to both the indoline and chromenone moieties have previously provided very low conductance values, and removing the alkynyl spacer has resulted in a total loss of conductance. An orthogonal T-shaped approach to single-molecule junctions incorporating spiropyran moieties in which the conducting pathway lies orthogonal to the molecule backbone is described and characterized. This approach has provided singlemolecule conductance features with good correlation to molecular length. Additional higher conducting states are accessible using switching induced by UV light or protonation. Theoretical modeling demonstrates that upon (photo)chemical isomerization to the merocyanine, two cooperating phenomena increase conductance: release of steric hindrance allows the conductance pathway to become more planar (raising the mid-bandgap transmission) and a bound state introduces sharp interference near the Fermi level of the electrodes similarly responding to the change in state. This design step paves the way for future use of spiropyrans in single-molecule devices and electrosteric switches.