Single-molecule Junctions Research Articles

Azaindole: A Candidate Anchor for Regulating Charge Polarity and Inducing Resonance Transmission at the Fermi Level via Dehydrogenation.

Tuning the polarity of charge carriers is essential for designing molecular logic devices in molecular electronics. In this study, the electrical transport properties of a family of azaindole-anchored single-molecule junctions have been investigated using density functional theory combined with the nonequilibrium Green's function method. The obtained results reveal that dehydrogenation is an effective method for reversing the polarity of charge carriers. The molecular junctions based on the entire azaindole unit are n-type and contain electrons as the principal charge carriers, whereas the dehydrogenated junctions are p-type and contain holes as the main carriers. Furthermore, the azaindole anchors undergo a transition from an electron-rich to an electron-deficient state due to dehydrogenation, which is the original cause of the charge carrier polarity conversion. Dehydrogenated molecular junctions also exhibit the Fermi pinning effect and a sharp highest occupied molecular orbital (HOMO) resonance peak at the Fermi level. In addition, using Pt electrodes instead of Au electrodes is a means of producing a HOMO resonance peak a for azaindole-based molecular junctions. This work demonstrates the enormous potential of utilizing azaindole-anchored molecular junctions for the implementation of molecular logic and multifunctional molecular devices.

Photoconductance Induced by Excited-State Intramolecular Proton Transfer (ESIPT) in Single-Molecule Junctions.

Excited-state intramolecular Proton Transfer (ESIPT) molecules have been drawing considerable attention due to their unique photophysical properties and potential applications in optoelectronic devices. Although ground and excited-state tautomerism in various proton transfer systems associated with ESIPT has been extensively studied both experimentally and theoretically, the charge-transport characteristics of ESIPT molecules at the single-molecule level has been little investigated. In this work, scanning tunneling microscope-based fixed junction technique (STM-FJ) is employed with theoretical calculations to explore the electronic properties of SMe-PhOH (with ESIPT properties), together with its photoconductance induced by ESIPT photocycle processes under continuous light illumination (254/275/295/310nm). The conductance variation of SMe-PhOH with different UV wavelengths exhibits a continuous photoconductance distribution, which is highly consistent with the results of its UV-vis absorption spectrum. Theoretical calculations indicate that the interaction between localized HOMO and delocalized LUMO of SMe-PhOH K*-state gives rise to Fano resonance, thereby leading to enhanced conductance compared with its E-state. It reveals the microscopic mechanism of ESIPT process at the nanoscale and provides a constructive perspective for optimizing the photoresponsive properties of ESIPT-type molecules, as well as designing high-performance single-molecule devices.

Boosting the Photoresponse of Azobenzene Single-Molecule Junctions via Mechanical Interlock and Dynamic Anchor.

As the most classic photoisomerization system, azobenzene has been widely utilized as a building unit in various photoswitching applications. However, attempts to build azobenzene-based single-molecule photoswitches have met with limited success, giving low on/off ratios. Herein, we demonstrate two designs of azobenzene-based photoresponsive single-molecule junctions, based on mechanically interlocked diazocine and azobenzene-based dynamic anchors, respectively. Molecular conductance measurements using the scanning tunneling microscope breaking junction (STMBJ) technique revealed dramatic conductance changes upon photoillumination, achieving a high on/off ratio of ∼3.7. Using density functional theory (DFT), we revealed peculiar quantum interference (QI) effects in the diazocine molecular switch, indicating that diazocine is an excellent candidate for molecular photoswitches. The asymmetric azobenzene devices with a dynamic anchor exhibit switching behavior between a fully off state and a highly conductive state associated with the trans/cis conformation transition. The findings of this work not only present the design and development of functional molecular devices based on azobenzene units but also provide insight into the fundamental properties of light-induced quantum interference in azobenzene-based molecular devices.

Exceptional Field Effect and Negative Differential Conductance in Spiro-Conjugated Single-Molecule Junctions.

The advancement of molecular electronics endeavors to build miniaturized electronic devices using molecules as the key building blocks by harnessing their internal structures and electronic orbitals. To date, linear planar conjugated or cross-conjugated molecules have been extensively employed in the fabrication of single-molecule devices, benefiting from their good conductivity and compatibility with electrode architectures. However, the development of multifunctional single-molecule devices, particularly those with unique charge transport properties, necessitates a more rigorous selection of molecular materials. Among different assortments of molecules suited for the construction of molecular circuits, Spiro-conjugated structures, specifically spirobifluorene derivatives, stand out as promising candidates due to their distinctive electronic properties. In this work, we focus on the charge transport characteristics of Spiro-conjugated molecules sandwiched between graphene nanogaps. Experiments reveal significant Coulomb blockade and distinct negative differential conductance effects. Beyond two-terminal device measurements, solid-state gate electrodes are utilized to create single-molecule transistors, successfully modulating the molecular energy levels to achieve an on/off ratio exceeding 1000. This endeavor not only offers valuable insights into the design and fabrication of future practical molecular devices, blessed with enhanced performance and functionality, but also presents a new paradigm for the investigation of fundamental physical phenomena.

Single-Molecule Conductance of Neutral Closed-Shell and Open-Shell Diradical Indenofluorenes.

Organic diradicals are highly promising candidates as future components in molecular electronic and spintronic devices because of their low spin-orbit coupling. To advance toward final circuit realizations, a thorough knowledge of the behavior of diradicals within a single-molecule junction framework is imperative. In this work, we have measured for the first time the single-molecule conductance of a neutral open-shell diradical compound, a [2,1-b] isomer of indenofluorene (IF). Our results reveal that the conductance of the [2,1-b] isomer is about 1 order of magnitude higher than that of the corresponding closed-shell regioisomer [1,2-b] IF. This is significant, as it fundamentally demonstrates the possibility of forming stable single-molecule junctions using neutral diradical compounds which are also highly conducting. This opens up a new approach to the development of externally addressable spintronic devices operable at room temperature.

Electrical monitoring of single-event protonation dynamics at the solid-liquid interface and its regulation by external mechanical forces

Detecting chemical reaction dynamics at solid-liquid interfaces is important for understanding heterogeneous reactions. However, there is a lack of exploration of interface reaction dynamics from the single-molecule perspective, which can reveal the intrinsic reaction mechanism underlying ensemble experiments. Here, single-event protonation reaction dynamics at a solid-liquid interface are studied in-situ using single-molecule junctions. Molecules with amino terminal groups are used to construct single-molecule junctions. An interfacial cationic state present after protonation is discovered. Real-time electrical measurements are used to monitor the reversible reaction between protonated and deprotonated states, thereby revealing the interfacial reaction mechanism through dynamic analysis. The protonation reaction rate constant has a linear positive correlation with proton concentration, whereas the deprotonation reaction rate constant has a linear negative correlation. In addition, external mechanical forces can effectively regulate the protonation reaction process. This work provides a single-molecule perspective for exploring interface science, which will contribute to the development of heterogeneous catalysis and electrochemistry.

Single-Molecule Conductance of Staffanes.

We report the first conductance measurements of [n]staffane oligomers in single-molecule junctions. Our studies reveal two quantum transport characteristics unique to staffanes that emerge from their strained bicyclic structure. First, though staffanes are composed of weakly conjugated C-C σ-bonds, staffanes carry a shallower conductance decay value (β = 0.84 ± 0.02 n-1) than alkane chain analogs (β = 0.96 ± 0.03 n-1) when measured with the scanning tunneling microscopy break junction (STM-BJ) technique. Staffanes aremore conductive than other σ-bonded organic backbones in the literature on a per atom basis. Density functional theory calculations suggest staffane backbones are effective conduits for charge transport because their significant bicyclic ring strain destabilizes the HOMO-2 energy, aligning it more closely with the Fermi energy as oligomer order increases. Second, the monostaffane is significantly lower conducting than expected. DFT calculations suggest that short monostaffanes sterically enforce insulating gauche interelectrode orientations over syn orientations. Meanwhile,[2-5]staffane wires may accommodate axial mechanical strain by "rod-bending". These findings show for the first time how bicyclic ring strain can enhance charge transmission in saturated molecular wires. These studies showcase the STM-BJ technique as a valuable tool for uncovering the stereoelectronic proclivities of molecules at material interfaces.

Bias switching in single-molecule junctions through destructive quantum interference

Highly nonlinear current-voltage (I-V) characteristics in single-molecule junctions based on destructive quantum interference (DQI) effects are key to realizing bias-controlled molecular switches. Using first-principles quantum transport calculations, we investigated the charge transport properties of 1,4-diphenyl-2,3-dioxa-7-tellurabicyclo(DPDT) coupled to gold electrodes via cyanide (-CN), isocyanide (-NC) and pyridyl (-PY) anchoring groups, respectively. We demonstrated that there are DQI effects between LUMO and LUMO+1 of the opposite phase in the three junctions. It was revealed that the p orbital of the tellurium atom can localize HOMO orbitals on central units of molecular systems, and weaken the amplitude of LUMO relative to LUMO+1. This eliminates the constructive quantum interference (CQI) between HOMO and LUMO, but enhances the DQI between LUMO and LUMO+1 near the Fermi energy level of gold electrodes (EF). As a result, the three molecular junctions dominated by two LUMOs exhibit extremely high nonlinear I-V characteristics, contributing to a current at a high bias (±0.8 V) >170 times larger than that at a low bias (±0.2 V). Our findings provide a potentially stable and low-loss bias switching in single-molecule junctions.

Covalent Au-C Contact Formation and C-C Homocoupling Reaction from Organotin Compounds in Single-Molecule Junctions.

Formation of new chemical species has been achieved under an electric field by the use of the scanning tunneling microscope break junction technique, yet simultaneous implementation of catalytic reactions both at the organic/metal interface and in the bulk solution remains a challenging task. Herein, we show that n-butyl-substituted organotin-terminated benzene undergoes both an efficient cleavage of the terminal tributyltin group to form a covalent Au-C bond and a homocoupling reaction to yield biphenyl product when subjected to an electric field in the vicinity to Au electrodes. By using ex situ characterization of high-performance liquid chromatography with an UV-vis detector, we demonstrate that the homocoupling reaction can occur with high efficiency under an extremely low tip bias voltage of ∼5 mV. Additionally, we show that the efficiency of the homocoupling reaction varies significantly in different solvents; the choice of the solvent proves to be one of the methods for modulating this reaction. By synthesizing and testing varied molecular backbone structures, we show that an extended biphenyl backbone undergoes homocoupling to form a quarterphenylene backbone, and the C-C coupling reactions are prohibited when additional aurophilic or bulky chemical groups that exhibit a steric blockage are introduced.

A Helicene-Based Single-Molecule Inductor and Capacitor with Frequency-Dependent Charge-Transport Pathways.

Despite extensive studies has been explored on single-molecule switches and rectifiers, the design of single-molecule inductors has not been explored due to the experimental challenges in the investigation of frequency-dependent charge transport at the single-molecule scale. In this study, we synthesized a helicene-based helical molecular wire and carried out meticulous single-molecule conductance measurements, combined with current-voltage (IV) studies with varying frequencies using the scanning tunneling microscope break junction (STM-BJ) technique. Our results reveal the formation of a single-molecule junction and highlight the unique behavior of the molecular wire in response to different alternating current (AC) varying frequencies. The transport of charges occurs selectively either through the coiled backbone of the conjugated helical structure or vertically via π-π stacking, depending on the frequency of the applied AC. Notably, our investigation demonstrates the functionality of the wire as an inductor at low frequencies, and a capacitor at high frequencies. This work lays the foundation for a systematic approach to designing, fabricating, and implementing single-molecule logic devices such as inductors and wave filters.

The Conductance and Thermopower Behavior of Pendent Trans-Coordinated Palladium(II) Complexes in Single-Molecule Junctions.

The present work provides insight into the effect of connectivity within isomeric 1,2-bis(2-pyridylethynyl)benzene (bpb) palladium complexes on their electron transmission properties within gold|single-molecule|gold junctions. The ligands 2,2'-((4,5-bis(hexyloxy)-1,2-phenylene)bis(ethyne-2,1-diyl))bis(4-(methylthio)pyridine) (Lm ) and 6,6'-((4,5-bis(hexyloxy)-1,2-phenylene)bis(ethyne-2,1-diyl))bis(3-(methylthio)pyridine) (Lp ) were synthesized and coordinated with PdCl2 to give the trans-Pd(Lmorp )Cl2 complexes. X-ray photoelectron spectroscopy (XPS) measurements shed light on the contacting modes of the molecules in the junctions. A combination of scanning tunneling microscopy-break junction (STM-BJ) measurements and density functional theory (DFT) calculations demonstrate that the typical lower conductance of meta- compared with para-connected isomers in a molecular junction was suppressed upon metal coordination. Simultaneously there was a modest increase in both conductance and Seebeck coefficient due to the contraction of the HOMO-LUMO gap upon metal coordination. It is shown that the low Seebeck coefficient is primarily a consequence of how the resonances shift relative to the Fermi energy.

Acid-Mediated Modulation of the Conductance of Diazapentalene Molecular Junctions.

We report an acid-mediated regulation of single-molecule junction conductance achieved using an electron-deficient unit, diazapentalene, functionalized with thiophene extending units and thiomethyl aurophilic terminal groups. This diazapentalene derivative exhibits a protonation reaction in the presence of trifluoroacetic acid, as characterized by UV-vis absorption spectroscopy, and the protonated species shows a voltage-dependent single-molecule conductance, which is not observed for the pristine molecules. Specifically, under a high bias voltage of 850 mV, we observe a conductance value for the protonated molecule larger than that for the deprotonated one by a factor of 4. Density functional theory-based transport calculations show a slight broadening of the HOMO and LUMO frontier orbitals, as well as a reduced HOMO-LUMO gap when the molecule becomes protonated; this implies an increased conductance under protonation that is consistent with the experimental conductance data. Our work demonstrates a new molecular design for versatile control of molecular conductance through the use of acid in the solvent environment.

Shape-persistent ladder molecules exhibit nanogap-independent conductance in single-molecule junctions.

Molecular electronic devices require precise control over the flow of current in single molecules. However, the electron transport properties of single molecules critically depend on dynamic molecular conformations in nanoscale junctions. Here we report a unique strategy for controlling molecular conductance using shape-persistent molecules. Chemically diverse, charged ladder molecules, synthesized via a one-pot multicomponent ladderization strategy, show a molecular conductance (d[log(G/G0)]/dx ≈ -0.1 nm-1) that is nearly independent of junction displacement, in stark contrast to the nanogap-dependent conductance (d[log(G/G0)]/dx ≈ -7 nm-1) observed for non-ladder analogues. Ladder molecules show an unusually narrow distribution of molecular conductance during dynamic junction displacement, which is attributed to the shape-persistent backbone and restricted rotation of terminal anchor groups. These principles are further extended to a butterfly-like molecule, thereby demonstrating the strategy's generality for achieving gap-independent conductance. Overall, our work provides important avenues for controlling molecular conductance using shape-persistent molecules.

Single-Molecule Cross-Plane Conductance of Polycyclic Aromatic Hydrocarbon Derivatives.

In the cross-plane single-molecule junctions, the correlation between molecular aromaticity and conductance remained puzzling. Cross-plane break junction (XPBJ) provides new insight into understanding the role of aromaticity and conjugation to molecules on charge transport through the planar molecules. In this work, we investigated the modulation of cross-plane charge transport in pyrene derivatives by hydrogenation and substituents based on the XPBJ method that differs from those used in-plane transport. We measured the electrical conductance of the hydrogenated derivatives of the pyrenes and found that hydrogenation reduces conductance, and the fully hydrogenated molecule has the lowest conductance. Conductance of pyrene derivatives increased after substitution by both electron-donating and electron-withdrawing groups. By calculating, the trend in decreased conductance of hydrogenated pyrene was found to be consistent with the change in aromaticity. Electron-withdrawing substituents reduce the aromaticity of the molecule and narrow the HOMO-LUMO gap, while electron-donating groups increase the aromaticity but also narrow the gap. Our work reveals the potential of fine-tuning the structure of the pyrene molecule to control the cross-plane charge transport through the single-molecule junctions.

Exploring Aromaticity Effects on Electronic Transport in Cyclo[n]carbon Single-Molecule Junctions.

Cyclo[n]carbon (Cn) is one member of the all-carbon allotrope family with potential applications in next-generation electronic devices. By employing first-principles quantum transport calculations, we have investigated the electronic transport properties of single-molecule junctions of Cn, with n = 14, 16, 18, and 20, connected to two bulk gold electrodes, uncovering notable distinctions arising from the varying aromaticities. For the doubly aromatic C14 and C18 molecules, slightly deformed complexes at the singlet state arise after bonding with one Au atom at each side; in contrast, the reduced energy gaps between the highest occupied and the lowest unoccupied molecular orbitals due to the orbital reordering observed in the doubly anti-aromatic C16 and C20 molecules lead to heavily deformed asymmetric complexes at the triplet state. Consequently, spin-unpolarized transmission functions are obtained for the Au-C14/18-Au junctions, while spin-polarized transmission appears in the Au-C16/20-Au junctions. Furthermore, the asymmetric in-plane π-type hybrid molecular orbitals of the Au-C16/20-Au junctions contribute to two broad but low transmission peaks far away from the Fermi level (Ef), while the out-of-plane π-type hybrid molecular orbitals dominate two sharp transmission peaks that are adjacent to Ef, thus resulting in much lower transmission coefficients at Ef compared to those of the Au-C14/18-Au junctions. Our findings are helpful for the design and application of future cyclo[n]carbon-based molecular electronic devices.

Quantum Dots and Molecular Junctions as Energy Filters for Thermal-to-Electric Energy Conversion

The thermoelectric conversion of heat into electricity requires a form of energy filtering, that allows hot electrons to pass while blocking cold electrons. The energy conversion efficiency is determined by the details of the energy filtering, with an infinitely sharp (delta function) transmission spectrum allowing near ideal (Carnot) efficiency. [1]I will introduce this concept and report on a proof-of-performance experiment based on a quantum dot embedded into a single, semiconductor nanowire. This near-ideal quantum-dot heat engine realized power production at maximum power with Curzon-Ahlborn efficiency as well more than 70% of Carnot efficiency at maximum efficiency settings [2].To further enhance efficiency at maximum power one wishes to shape the transmission function to allow a spectrum of warmer electrons to pass while still completely blocking cold electrons. This may be achieved by exploiting quantum interference phenomena to block low-energy electron transmission by destructive interference, and to thus sculpt the transmission function of quantum dots or molecular junctions.[4] In contrast to quantum dots, molecular junctions have the advantage that they can be used at room temperature and can be produced, in principle, cheaply and scalable. To systematically explore the effect of quantum interferences, we designed and synthesized a new class of porphyrins that are expected to feature destructive quantum interference in single molecule junctions with gold electrodes and may thus show high thermopower, as well as a control that does not. We performed detailed experimental single-molecule break-junction studies of conductance and thermopower on porphyrin molecular junctions. We find a somewhat better thermoelectric performance for the porphyrin where we expect destructive interference. However, the predicted large difference in conductance and thermopower is not supported by our experimental findings.[4]Finally, I will also briefly discuss the potential application of the concepts and systems presented here in hot-carrier photovoltaics, as an approach to increasing photovoltaic energy conversion efficiency beyond current limits.[1] T.E. Humphrey et al., Reversible Quantum Brownian Heat Engines for Electrons. Phys. Rev. Lett., 89, 116801 (2002)[2] M. Josefsson et al. A quantum-dot heat engine operated close to thermodynamic efficiency limits. Nature Nanotechn. 13, 920 (2018)[3] O Karlström et al. Increasing thermoelectric performance using coherent transport. Phys. Rev. B 84, 113415 (2011)[4] H. Xu et al. Electrical Conductance and Thermopower of β-Substituted Porphyrin Molecular Junctions Synthesis and Transport. JACS 145 , 23541 (2023) Figure 1

Effective Coupling Model to Treat the Odd-Even Effect on the Current-Voltage Response of Saturated Linear Carbon Chains Single-Molecule Junctions.

The calculation of the electrical charge transport properties of alkanes C n H 2n S 2 with (n = 4-11) was performed to understand the odd-even effect on its current-voltage response. The extended molecule and broadband limit models were used to describe the molecular junction and covalent coupling with the electrodes. It was shown that among the participating molecular orbitals, HOMO and HOMO-1 are the ones with the most charge transport contribution. Moreover, the odd-even effect is caused by the alternation of the eigenvalues of some frontier orbitals as a function of the number of carbons, especially the HOMO that dominates the electrical transport. It could also be noted that when the current is analyzed outside the resonance, the relationship with the number of carbons exponentially decays, confirming the reports in the literature. To the best of our knowledge, a first principle study of the odd-even effect in symmetric systems composed by linear saturated carbon chains covalently coupled to electrodes has not been reported yet.

An Infrared Nanospectroscopy Technique for the Study of Electric-Field-Induced Molecular Dynamics.

Static electric fields play a considerable role in a variety of molecular nanosystems as diverse as single-molecule junctions, molecules supporting electrostatic catalysis, and biological cell membranes incorporating proteins. External electric fields can be applied to nanoscale samples with a conductive atomic force microscopy (AFM) probe in contact mode, but typically, no structural information is retrieved. Here we combine photothermal expansion infrared (IR) nanospectroscopy with electrostatic AFM probes to measure nanometric volumes where the IR field enhancement and the static electric field overlap spatially. We leverage the vibrational Stark effect in the polymer poly(methyl methacrylate) for calibrating the local electric field strength. In the relevant case of membrane protein bacteriorhodopsin, we observe electric-field-induced changes of the protein backbone conformation and residue protonation state. The proposed technique also has the potential to measure DC currents and IR spectra simultaneously, insofar enabling the monitoring of the possible interplay between charge transport and other effects.

Interfacial Stereoelectronic Effect Induced by Anchoring Orientation.

Heterogeneous interfaces in most devices play a key role in the material performance. Exploring the atomic structure and electronic properties of metal-molecule interfaces is critical for various potential applications, such as surface sensing, molecular recognition, and molecular electronic devices. This study unveils a ubiquitous interfacial stereoelectronic effect in conjugated molecular junctions by combining first-principles simulation and scanning tunneling microscopy break junction technology. Single-molecule junctions with same-side interfacial anchoring (cis configuration) exhibit higher conductance than those with opposite-side interfacial anchoring (trans configuration). The cis and trans configurations can undergo reversible conversions, resulting in a conductance switching. The stability of these configurations can be adjusted by an electric field, achieving precise regulation of conductance states. Our findings provide important insights for designing high-quality materials and enhancing the device performance.

Direct flipping dynamics and quantized enrichment of chirality at single-molecule resolution.

Chirality is an important aspect of nature, and numerous macroscopic methods have been developed to understand and control chirality. For the chiral tertiary amines, their flexible flipping process makes it possible to achieve high chiral controllability without bond formation and breaking. Here, we present a type of stable chiral single-molecule devices formed by tertiary amines, using graphene-molecule-graphene single-molecule junctions. These single-molecule devices allow real-time, in situ, and long-time measurements of the flipping process of an individual chiral nitrogen center with high temporal resolution. Temperature- and bias voltage-dependent experiments, along with theoretical investigations, revealed diverse chiral intermediates, indicating the regulation of the flipping dynamics by energy-related factors. Angle-dependent measurements further demonstrated efficient enrichment of chiral states using linearly polarized light by a symmetry-related factor. This approach offers a reliable means for understanding the chirality's origin, elucidating microscopic chirality regulation mechanisms, and aiding in the design of effective drugs.