Intermolecular and Electrode-Molecule Bonding in a Single Dimer Junction of Naphthalenethiol as Revealed by Surface-Enhanced Raman Scattering Combined with Transport Measurements.

Electron transport through noncovalent interaction is of fundamental and practical importance in nanomaterials and nanodevices. Recent single-molecule studies employing single-molecule junctions have revealed unique electron transport properties through noncovalent interactions, especially those through a π-π interaction. However, the relationship between the junction structure and electron transport remains elusive due to the insufficient knowledge of geometric structures. In this article, we employ surface-enhanced Raman scattering (SERS) synchronized with current-voltage (I-V) measurements to characterize the junction structure, together with the transport properties, of a single dimer and monomer junction of naphthalenethiol, the former of which was formed by the intermolecular π-π interaction. The correlation analysis of the vibrational energy and electrical conductance enables identifying the intermolecular and molecule-electrode interactions in these molecular junctions and, consequently, addressing the transport properties exclusively associated with the π-π interaction. In addition, the analysis achieved discrimination of the interaction between the NT molecule and the Au electrode of the junction, i.e., Au-π interactions through-π coupling and though-space coupling. The power density spectra support the noncovalent character at the interfaces in the molecular junctions. These results demonstrate that the simultaneous SERS and I-V technique provides a unique means for the structural and electrical investigation of noncovalent interactions.

Unique Electrical Signature of Phosphate for Specific Single-Molecule Detection of Peptide Phosphorylation.

Single-molecule measurements of biomaterials bring novel insights into cellular events. For almost all of these events, post-translational modifications (PTMs), which alter the properties of proteins through their chemical modifications, constitute essential regulatory mechanisms. However, suitable single-molecule methodology to study PTMs is very limited. Here we show single-molecule detection of peptide phosphorylation, an archetypal PTM, based on electrical measurements. We found that the phosphate group stably bridges a nanogap between metal electrodes and exhibited high electrical conductance, which enables specific single-molecule detection of peptide phosphorylation. The present methodology paves the way to single-molecule studies of PTMs, such as single-molecule kinetics for enzymatic modification of proteins as shown here.

Principal Component Analysis of Surface-Enhanced Raman Scattering Spectra Revealing Isomer-Dependent Electron Transport in Spiropyran Molecular Junctions: Implications for Nanoscale Molecular Electronics.

The characterization of single-molecule structures could provide significant insights into the operation mechanisms of functional devices. Structural transformation via isomerization has been extensively employed to implement device functionalities. Although single-molecule identification has recently been achieved using near-field spectroscopy, discrimination between isomeric forms remains challenging. Further, the structure-function relationship at the single-molecule scale remains unclear. Herein, we report the observation of the isomerization of spiropyran in a single-molecule junction (SMJ) using simultaneous surface-enhanced Raman scattering (SERS) and conductance measurements. SERS spectra were used to discriminate between isomers based on characteristic peaks. Moreover, conductance measurements, in conjunction with the principal component analysis of the SERS spectra, clearly showed the isomeric effect on the conductance of the SMJ.

Structural Asymmetry of Metallic Single-Atom Contacts Detected by Current-Voltage Characteristics.

The complex behavior of the simplest atomic-scale conductors indicates that the electrode structure itself is significant in the design of future nanoscale devices. In this study, the structural asymmetry of metallic atomic contacts formed between two macroscopic Au electrodes at room temperature was investigated. Characteristic signatures of the structural asymmetries were detected by fast current-voltage (I-V) measurements with a time resolution of approximately 100 µs. Statistical analysis of more than 300,000 I-V curves obtained from more than 1000 contact-stretching processes demonstrates that the current rectification properties are correlated with the conductance of the nanocontacts. A substantial suppression of the variation in current rectification was observed for the atomic contacts with integer multiples of the conductance quantum. Statistical analysis of the time-resolved I-V curves revealed that the current rectification variations increased significantly from 500 µs onward before the breakage of the atomic contacts. Ab initio atomistic simulations of the stretching processes and corresponding I-V characteristics confirmed the magnitude of the rectification and related it to the structural asymmetries in the breakdown process of the junctions. Overall, we provide a better understanding of the interplay between geometric and electronic structures at atomically defined metal-metal interfaces by probing charge transport properties in extremely sensitive nanocontacts.

Surface-Enhanced Raman Scattering Stimulated by Strong Metal-Molecule Interactions in a C60 Single-Molecule Junction.

Specifying the geometric and electronic structures of a metal-molecule interface at the single-molecule level is crucial for the improvement of organic electronics. A single-molecule junction (SMJ) can be used to investigate interfaces because it can be regarded as an elementary unit of the interface structure. Although considerable efforts have been made to this end, the detection of structural changes in SMJs associated with metal-molecule interactions remains challenging. In this study, we detected the surface-enhanced Raman scattering (SERS) signal originating from the metal-molecule interaction change induced by a local structural change in a C60 SMJ. This junction has attracted wide attention owing to its unique electronic and vibronic properties. We fabricated a C60 SMJ using a lithographically fabricated Au electrode and measured the SERS spectra along with the current-voltage (I-V) response. By continuous measurement of SERS for the C60 SMJ, we obtained SERS spectra dependent on the local structural change. The analysis of the I-V response revealed that the vibration energy shift originates from the change in the local structure for different Au-C60 interactions. Based on the discrimination of the states in accordance with the Au-C60 interaction, we found that the probability of SERS for geometry with a large Au-C60 interaction was enhanced.

Single-molecule junction spontaneously restored by DNA zipper.

The electrical properties of DNA have been extensively investigated within the field of molecular electronics. Previous studies on this topic primarily focused on the transport phenomena in the static structure at thermodynamic equilibria. Consequently, the properties of higher-order structures of DNA and their structural changes associated with the design of single-molecule electronic devices have not been fully studied so far. This stems from the limitation that only extremely short DNA is available for electrical measurements, since the single-molecule conductance decreases sharply with the increase in the molecular length. Here, we report a DNA zipper configuration to form a single-molecule junction. The duplex is accommodated in a nanogap between metal electrodes in a configuration where the duplex is perpendicular to the nanogap axis. Electrical measurements reveal that the single-molecule junction of the 90-mer DNA zipper exhibits high conductance due to the delocalized π system. Moreover, we find an attractive self-restoring capability that the single-molecule junction can be repeatedly formed without full structural breakdown even after electrical failure. The DNA zipping strategy presented here provides a basis for novel designs of single-molecule junctions.

Visualization of Thermal Transport Properties of Self-Assembled Monolayers on Au(111) by Contact and Noncontact Scanning Thermal Microscopy.

Thermal transport properties of patterned binary self-assembled monolayers (SAMs) on Au(111) were examined using scanning thermal microscopy (SThM) with both contact and noncontact methods. We fabricated two-dimensional (2D) patterns with two separate domains of n-hexadecanethiol/benzenethiol, benzenethiol/n-butanethiol, or n-hexadecanethiol/n-butanethiol. In the experimental setup, the efficiency of thermal transport from a SThM tip to the SAM surface can be evaluated in terms of the temperature change at the SThM tip. In the contact regime, where a SThM tip physically contacts the SAM surface, direct thermal transport through the SAM and radiation-based thermal transport through the space where SAMs exist may contribute to a drop in temperature at the tip. In the noncontact regime, thermal transport relies on radiation-based heat dissipation from the heated tip to the SAMs. 2D mapping of the spatial temperature distribution on SAMs reflects the difference in thermal transport properties of the two SAM domains. We found that the contact method is effective for visualizing the temperature contrast, which reflects the thermal transport properties of the constituent molecules when the domains of the SAMs have a similar height, while the noncontact method allows visualization of the temperature distribution, which is related to the height of each domain of the SAMs, rather than the chemical structures of the constituent molecules. Combination of contact and noncontact SThM enables 2D imaging of thermal transport properties and topographic imaging simultaneously and represents a new technique for investigating the thermal properties of materials surfaces, which is essential for nanoscale thermal management.

Control of dominant conduction orbitals by peripheral substituents in paddle-wheel diruthenium alkynyl molecular junctions.

Control of charge carriers that transport through the molecular junctions is essential for thermoelectric materials. In general, the charge carrier depends on the dominant conduction orbitals and is dominantly determined by the terminal anchor groups. The present study discloses the synthesis, physical properties in solution, and single-molecule conductance of paddle-wheel diruthenium complexes 1R having diarylformamidinato supporting ligands (DArF: p-R-C6H4-NCHN-C6H4-R-p) and two axial thioanisylethynyl conducting anchor groups, revealing unique substituent effects with respect to the conduction orbitals. The complexes 1R with a few different aryl substituents (R = OMe, H, Cl, and CF3) were fully characterized by spectroscopic and crystallographic analyses. The single-molecule conductance determined by the scanning tunneling microscope break junction (STM-BJ) technique was in the 10-5 to 10-4 G 0 region, and the order of conductance was 1OMe > 1CF3 ≫ 1H ∼ 1Cl, which was not consistent with the Hammett substituent constants σ of R. Cyclic voltammetry revealed the narrow HOMO-LUMO gaps of 1R originating from the diruthenium motif, as further supported by the DFT study. The DFT-NEGF analysis of this unique result revealed that the dominant conductance routes changed from HOMO conductance (for 1OMe) to LUMO conductance (for 1CF3). The drastic change in the conductance properties originates from the intrinsic narrow HOMO-LUMO gaps.

Water Splitting Induced by Visible Light at a Copper-Based Single-Molecule Junction.

Water splitting is an essential process for converting light energy into easily storable energy in the form of hydrogen. As environmentally preferable catalysts, Cu-based materials have attracted attention as water-splitting catalysts. To enhance the efficiency of water splitting, a reaction process should be developed. Single-molecule junctions (SMJs) are attractive structures for developing these reactions because the molecule electronic state is significantly modulated, and characteristic electromagnetic effects can be expected. Here, water splitting is induced at Cu-based SMJ and the produced hydrogen is characterized at a single-molecule scale by employing electron transport measurements. After visible light irradiation, the conductance states originate from Cu/hydrogen molecule/Cu junctions, while before irradiation, only Cu/water molecule/Cu junctions were observed. The vibration spectra obtained from inelastic electron tunneling spectroscopy combined with the first-principles calculations reveal that the water molecule trapped between the Cu electrodes is decomposed and that hydrogen is produced. Time-dependent and wavelength-dependent measurements show that localized-surface plasmon decomposes the water molecule in the vicinity of the junction. These findings indicate the potential ability of Cu-based materials for photocatalysis.

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.

Organometallic Molecular Wires with Thioacetylene Backbones, trans-{RS-(C≡C)n }2 Ru(phosphine)4 : High Conductance through Non-Aromatic Bridging Linkers.

In this work, the design, synthesis, and single-molecule conductance of ethynyl- and butadiynyl-ruthenium molecular wires with thioether anchor groups [RS=n-C6 H13 S, p-tert-Bu-C6 H4 S), trans-{RS-(C≡C)n }2 Ru(dppe)2 (n=1 (1R ), 2 (2R ); dppe: 1,2-bis(diphenylphosphino)ethane) and trans-(n-C6 H13 S-C≡C)2 Ru{P(OMe)3 }4 3hex ] are reported. Scanning tunneling microscope break-junction study has revealed conductance of the organometallic molecular wires with the thioacetylene backbones higher than that of the related organometallic wires having arylethynylruthenium linkages with the sulfur anchor groups, trans-{p-MeS-C6 H4 -(C≡C)n }2 Ru(phosphine)4 4n (n=1, 2) and trans-(Th-C≡C)2 Ru(phosphine)4 5 (Th=3-thienyl). It should be noted that the molecular junctions constructed from the butadiynyl wire 2R , trans-{Au-RS-(C≡C)2 }2 Ru(dppe)2 (Au: gold metal electrode), show conductance comparable to that of the covalently linked polyynyl wire with the similar molecular length, trans-{Au-(C≡C)3 }2 Ru(dppe)2 63 . The DFT non-equilibrium Green's function (NEGF) study supports the highly conducting nature of the thioacetylene molecular wires through HOMO orbitals.

Structure and Electron Transport at Metal Atomic Junctions Doped with Dichloroethylene.

The front cover artwork was provided by the group of Prof. Nishino, Tokyo Institute of Technology. The image depicts the investigation of the structure and electron transport of the Au, Ag, Cu, Ni, Fe, and Pd atomic junctions doped with dichloroethylene. Read the full text of the Article at 10.1002/cphc.201900988.

Selective formation of molecular junctions with high and low conductance states by tuning the velocity of electrode displacement.

A single-molecule junction of 1,4-di(4-pyridyl)benzene (DPB) was prepared in a nano-gap between two Au electrodes using the scanning tunnelling microscopy-based break junction method (STM-BJ). Electric conductance and current versus bias voltage (I-V) measurements during the pulling and pushing processes of DPB single-molecule junctions revealed that high (H) and low (L) conductance states formed in both the pulling and pushing processes. Analysis of the I-V curves based on a single-level model indicated that the difference in conductivity of the H and L states mainly arises from high and low metal-molecule electric coupling in the junction. We demonstrated the controllable formation of H and L conductance states by simply tuning the velocity of electrode displacement in the pushing process. In the pulling process, both H and L states formed regardless of the velocity (v) of electrode displacement, while in the pushing process, H and L states could be selectively fabricated by using low (v = 16 nm s-1) and high (v = 64 nm s-1) velocities of displacement, respectively. This study provides a simple approach to selectively fabricate high and low conductance states by fine tuning of the electrode displacement.

Elementary processes of DNA surface hybridization resolved by single-molecule kinetics: implication for macroscopic device performance.

Direct monitoring of single-molecule reactions has recently become a promising means of mechanistic investigation. However, the resolution of reaction pathways from single-molecule experiments remains elusive, primarily because of interference from extraneous processes such as bulk diffusion. Herein, we report a single-molecule kinetic investigation of DNA hybridization on a metal surface, as an example of a bimolecular association reaction. The tip of the scanning tunneling microscope (STM) was functionalized with single-stranded DNA (ssDNA), and hybridization with its complementary strand on an Au(111) surface was detected by the increase in the electrical conductance associated with the electron transport through the resulting DNA duplex. Kinetic analyses of the conductance changes successfully resolved the elementary processes, which involve not only the ssDNA strands and their duplex but also partially hybridized intermediate strands, and we found an increase in the hybridization efficiency with increasing the concentration of DNA in contrast to the knowledge obtained previously by conventional ensemble measurements. The rate constants derived from our single-molecule studies provide a rational explanation of these findings, such as the suppression of DNA melting on surfaces with higher DNA coverage. The present methodology, which relies on intermolecular conductance measurements, can be extended to a range of single-molecule reactions and to the exploration of novel chemical syntheses.

Structure and Electron Transport at Metal Atomic Junctions Doped with Dichloroethylene.

We have investigated the structure and electron transport at dichloroethylene-doped metal atomic junctions at low temperatures (20 K) in ultra-high vacuum, using Fe, Ni, Pd, Cu, Ag, and Au. The metal atomic junctions were fabricated using the mechanically controllable break junction technique. After introducing the dichloroethylene (DCE), the conductance behavior of Fe, Ni, and Pd junctions was considerably changed, whereas little change was observed for Cu, Ag, and Au. For the Pd and Cu junctions, a clear peak was observed in their conductance histograms, showing that the single-molecule junction was selectively formed. To investigate the structure of the metal atomic junctions further, their plateau lengths were analyzed. The length analysis revealed that the Au atomic wire was elongated, and the metal atomic wires were formed for the other transition metals: those that do not normally form metal atomic wires without DCE doping, as DCE adsorption stabilized the metal atomic states. There is a strong interaction between DCE and the metals, where DCE supports the formation of the metal atomic wire for Fe, Ni, and Pd.

Kinetic investigation of a chemical process in single-molecule junction.

Herein, we report on the kinetic investigation for the breakdown of single-molecule junctions. Current through the junctions was measured as a function of time to elucidate their lifetimes. The analysis of the lifetimes revealed that the breakdown reaction obeys first-order reaction kinetics, and the rate constants determined from the analysis were found to reflect the stability of the junctions.

Electric-Field-Controllable Conductance Switching of an Overcrowded Ethylene Self-Assembled Monolayer.

Molecular isomerism has been discussed from the viewpoint of the tiniest switch and memory elements in electronics. Here, we report an overcrowded ethylene-based molecular conductance switch, which fulfills all the essential requirements for implementation into electronic devices, namely, electric-field-controllable reversible conductance change with a molecular-level spatial resolution, robust conformational bistability under ambient conditions, and ordered monolayer formation on electrode surfaces. The conformational state of this overcrowded ethylene, represented by a folded or twisted conformer, is susceptible to external environments. Nanoscopic measurements using scanning tunneling microscopy techniques, together with theoretical simulations, revealed the electronic properties of each conformer adsorbed on Au(111). While the twisted conformer prevails in the molecularly dispersed state, upon self-assembly into a monolayer, a two-dimensional network structure of the folded conformer is preferentially formed due to particular intermolecular interaction. In the monolayer state, folded-to-twisted and its reverse isomerization can be controlled by the modulation of electric fields.

Identifying the molecular adsorption site of a single molecule junction through combined Raman and conductance studies.

Single-molecule junctions are ideal test beds for investigating the fundamentals of charge transport at the nanoscale. Conducting properties are strongly dependent on the metal-molecule interface geometry, which, however, is very poorly characterized due to numerous experimental challenges. We report on a new methodology for characterizing the adsorption site of single-molecule junctions through the combination of surface enhanced Raman scattering (SERS), current-voltage (I-V) curve measurements, and density functional theory simulations. This new methodology discriminates between three different adsorption sites for benzenedithiol and aminobenzenethiol junctions, which cannot be identified by solo measurements of either SERS or I-V curves. Using this methodology, we determine the interface geometry of these two prototypical molecules at the junction and its time evolution. By modulating the applied voltage, we can change and monitor the distribution of adsorption sites at the junction.

Tuneable single-molecule electronic conductance of C60 by encapsulation.

It has been demonstrated that the single-molecule transport properties of fullerene C60 can be modulated by encapsulating endohedral species, i.e. Li+ and H2O, which exhibit different degrees of van der Waals interactions with the C60 cage. Single-molecule junctions were prepared between the gaps of Au electrodes using a break junction technique. Encapsulation of H2O inside the cage caused a slight decrease in the electronic conductivity relative to that of pristine C60. This is in sharp contrast to Li+ encapsulation, which results in a twofold-to-fourfold increase in the conductivity. The electronic couplings between the C60 cage and the Au electrodes were weakly dependent on the endohedral species in the cage, though the molecular orbital energy levels were remarkably modulated upon encapsulation.

Highly Reproducible Formation of a Polymer Single-Molecule Junction for a Well-Defined Current Signal.

Single-molecule devices attract much interest in the development of nanoscale electronics. Although a variety of functional single molecules for single-molecule electronics have been developed, there still remains the need to implement sophisticated functionalization toward practical applications. Given its superior functionality encountered in macroscopic materials, a polymer could be a useful building block in the single-molecule devices. Therefore, a molecular junction composed of polymer has now been created. Furthermore, an automated algorithm was developed to quantitatively analyze the tunneling current through the junction. Quantitative analysis revealed that the polymer junction exhibits a higher formation probability and longer lifetime than its monomer counterpart. These results suggest that the polymer provides a unique opportunity to design both stable and highly functional molecular devices for nanoelectronics.