Photooxidation driven formation of Fe-Au linked ferrocene-based single-molecule junctions.

Metal-metal contacts, though not yet widely realized, may provide exciting opportunities to serve as tunable and functional interfaces in single-molecule devices. One of the simplest components which might facilitate such binding interactions is the ferrocene group. Notably, direct bonds between the ferrocene iron center and metals such as Pd or Co have been demonstrated in molecular complexes comprising coordinating ligands attached to the cyclopentadienyl rings. Here, we demonstrate that ferrocene-based single-molecule devices with Fe-Au interfacial contact geometries form at room temperature in the absence of supporting coordinating ligands. Applying a photoredox reaction, we propose that ferrocene only functions effectively as a contact group when oxidized, binding to gold through a formal Fe3+ center. This observation is further supported by a series of control measurements and density functional theory calculations. Our findings extend the scope of junction contact chemistries beyond those involving main group elements, lay the foundation for light switchable ferrocene-based single-molecule devices, and highlight new potential mechanistic function(s) of unsubstituted ferrocenium groups in synthetic processes.

Determining Transmission Characteristics from Shot-Noise-Driven Electroluminescence in Single-Molecule Junctions.

Biased metal-molecule-metal junctions emit light through electroluminescence, a phenomenon at the intersection of molecular electronics and nanoplasmonics. This can occur when the junction plasmon mode is excited by inelastic electron current fluctuations. Here, we simultaneously measure the conductance and electroluminescence intensity from single-molecule junctions with time resolution in a solution environment at room temperature. We use current versus bias data to determine the molecular junction transport parameters and then relate these to the expected current shot noise. We find that the electroluminescence signal accurately matches the theoretical prediction of shot-noise-driven emission in a large fraction of the molecular junctions studied. This introduces a novel experimental method for qualitatively estimating finite-frequency shot noise in single-molecule junctions under ambient conditions. We further demonstrate that electroluminescence can be used to obtain the level alignment of the frontier orbital dominating transport in the molecular junction.

Solvent-Mediated Modulation of the Au-S Bond in Dithiol Molecular Junctions.

Gold-dithiol molecular junctions have been studied both experimentally and theoretically. However, the nature of the gold-thiolate bond as it relates to the solvent has seldom been investigated. It is known that solvents can impact the electronic structure of single-molecule junctions, but the correlation between the solvent and dithiol-linked single-molecule junction conductance is not well understood. We study molecular junctions formed with thiol-terminated phenylenes from both 1-chloronaphthalene and 1-bromonaphthalene solutions. We find that the most probable conductance and the distribution of conductances are both affected by the solvent. First-principles calculations show that junction conductance depends on the binding configurations (adatom, atop, and bridge) of the thiolate on the Au surface, as has been shown previously. More importantly, we find that brominated solvents can restrict the binding of thiols to specific Au sites. This mechanism offers new insight into the effects of the solvent environment on covalent bonding in molecular junctions.

Effective Gating in Single-Molecule Junctions through Fano Resonances.

The successful incorporation of molecules as active circuit elements relies on the ability to tune their electronic properties through chemical design. A synthetic strategy that has been used to manipulate and gate circuit conductance involves attaching a pendant substituent along the molecular conduction pathway. However, such a chemical gate has not yet been shown to significantly modify conductance. Here, we report a novel series of triarylmethylium and triangulenium carbocations gated by different substituents coupled to the delocalized conducting orbitals on the molecular backbone through a Fano resonance. By changing the pendant substituents to modulate the position of the Fano resonance and its coupling to the conducting orbitals, we can regulate the junction conductance by a remarkable factor of 450. This work thus provides a new design principle to enable effective chemical gating of single-molecule devices toward effective molecular transistors.

Radical Single-Molecule Junctions.

Radicals are unique molecular systems for applications in electronic devices due to their open-shell electronic structures. Radicals can function as good electrical conductors and switches in molecular circuits while also holding great promise in the field of molecular spintronics. However, it is both challenging to create stable, persistent radicals and to understand their properties in molecular junctions. The goal of this Perspective is to address this dual challenge by providing design principles for the synthesis of stable radicals relevant to molecular junctions, as well as offering current insight into the electronic properties of radicals in single-molecule devices. By exploring both the chemical and physical properties of established radical systems, we will facilitate increased exploration and development of radical-based molecular systems.

Designing Long and Highly Conducting Molecular Wires with Multiple Nontrivial Topological States.

Molecular one-dimensional topological insulators (1D TIs), described by the Su-Schrieffer-Heeger (SSH) model, are a new class of molecular electronic wires whose low-energy topological edge states endow them with high electrical conductivity. However, when these 1D TIs become long, the high conductance is not sustained because the coupling between the edge states decreases with increasing length. Here, we present a new design where we connect multiple short 1D SSH TI units linearly or in a cycle to create molecular wires with a continuous topological state density. Using a tight-binding method, we show that the linear system gives a length-independent conductance. The cyclic systems show an interesting odd-even effect, with unit transmission in the topological limit, but zero transmission in the trivial limit. Furthermore, based on our calculations, we predict that these systems can support resonant transmission with a quantum of conductance. We can further expand these results to phenylene-based linear and cyclic 1D TI systems and confirm the length-dependent conductance in such systems.

Alkane Solvent-Derived Acylation Reaction Driven by Electric Fields.

Electric field acceleration of alkyl hydroperoxide activation to acylate amines in the scanning tunneling microscope-based break-junction is reported. Alkyl hydroperoxide mixtures, generated from hydrocarbon autoxidation in air, were found to be competent reagents for the functionalization of gold surfaces. Intermolecular coupling on the surface in the presence of amines was observed, yielding normal alkylamides. This novel mode of alkyl hydroperoxide activation to generate acylium equivalents was found to be responsive to the magnitude of the bias in the break junction, indicating an electric field influence on this novel reactivity.

Electric fields drive bond homolysis.

Electric fields have been used to control and direct chemical reactions in biochemistry and enzymatic catalysis, yet directly applying external electric fields to activate reactions in bulk solution and to characterize them ex situ remains a challenge. Here we utilize the scanning tunneling microscope-based break-junction technique to investigate the electric field driven homolytic cleavage of the radical initiator 4-(methylthio)benzoic peroxyanhydride at ambient temperatures in bulk solution, without the use of co-initiators or photochemical activators. Through time-dependent ex situ quantification by high performance liquid chromatography using a UV-vis detector, we find that the electric field catalyzes the reaction. Importantly, we demonstrate that the reaction rate in a field increases linearly with the solvent dielectric constant. Using density functional theory calculations, we show that the applied electric field decreases the dissociation energy of the O-O bond and stabilizes the product relative to the reactant due to their different dipole moments.

Topological Radical Pairs Produce Ultrahigh Conductance in Long Molecular Wires.

Molecular one-dimensional topological insulators (1D TIs), which conduct through energetically low-lying topological edge states, can be extremely highly conducting and exhibit a reversed conductance decay, affording them great potential as building blocks for nanoelectronic devices. However, these properties can only be observed at the short length limit. To extend the length at which these anomalous effects can be observed, we design topological oligo[n]emeraldine wires using short 1D TIs as building blocks. As the wire length increases, the number of topological states increases, enabling an increased electronic transmission along the wire; specifically, we show that we can drive over a microampere current through a single ∼5 nm molecular wire, appreciably more than what has been observed in other long wires reported to date. Calculations and experiments show that the longest oligo[7]emeraldine with doped topological states has over 106 enhancements in the transmission compared to its pristine form. The discovery of these highly conductive, long organic wires helps overcome a fundamental hurdle to implementing molecules in complex, nanoscale circuitry: their structures become too insulating at lengths that are useful in designing nanoscale circuits.

Voltage-Modulated van der Waals Interaction in Single-Molecule Junctions.

Understanding how molecular geometry affects the electronic properties of single-molecule junctions experimentally has been challenging. Typically, metal-molecule-metal junctions are measured using a break-junction method where electrode separation is mechanically evolving during measurement. Here, to probe the impact of the junction geometry on conductance, we apply a sinusoidal modulation to the molecular junction electrode position. Simultaneously, we probe the nonlinearity of the current-voltage characteristics of each junction through a modulation in the applied bias at a different frequency. In turn, we show that junctions formed with molecules that have different molecule-electrode interfaces exhibit statistically distinguishable Fourier-transformed conductances. In particular, we find a marked bias dependence for the modulation of junctions where transmission is mediated thorough the van der Waals (vdW) interaction. We attribute our findings to voltage-modulated vdW interactions at the single-molecule level.

Interfacial electric fields catalyze Ullmann coupling reactions on gold surfaces.

The electric fields created at solid-liquid interfaces are important in heterogeneous catalysis. Here we describe the Ullmann coupling of aryl iodides on rough gold surfaces, which we monitor in situ using the scanning tunneling microscope-based break junction (STM-BJ) and ex situ using mass spectrometry and fluorescence spectroscopy. We find that this Ullmann coupling reaction occurs only on rough gold surfaces in polar solvents, the latter of which implicates interfacial electric fields. These experimental observations are supported by density functional theory calculations that elucidate the roles of surface roughness and local electric fields on the reaction. More broadly, this touchstone study offers a facile method to access and probe in real time an increasingly prominent yet incompletely understood mode of catalysis.

Electric-field-induced coupling of aryl iodides with a nickel(0) complex.

The formation of carbon-carbon bonds with transition metal reagents serves as a cornerstone of organic synthesis. Here, we show that the reactivity of an otherwise kinetically inert transition metal complex can be induced by an external electric field to affect a coupling reaction. These results highlight the importance of electric field effects in reaction chemistry and offers a new strategy to modulate organometallic reactivity.

Correction: Electric-field-induced coupling of aryl iodides with a nickel(0) complex.

Correction for 'Electric-field-induced coupling of aryl iodides with a nickel(0) complex' by Nicholas M. Orchanian et al., Chem. Commun., 2022, https://doi.org/10.1039/d2cc03671a.

Reversed Conductance Decay of 1D Topological Insulators by Tight-Binding Analysis.

Reversed conductance decay describes increasing conductance of a molecular chain series with increasing chain length. Realizing reversed conductance decay is an important step toward making long and highly conducting molecular wires. Recent work has shown that one-dimensional topological insulators (1D TIs) can exhibit reversed conductance decay due to their nontrivial edge states. The Su-Schrieffer-Heeger (SSH) model for 1D TIs relates to the electronic structure of these isolated molecules but not their electron transport properties as single-molecule junctions. Herein, we use a tight-binding approach to demonstrate that polyacetylene and other diradicaloid 1D TIs show a reversed conductance decay at the short chain limit. We explain these conductance trends by analyzing the impact of the edge states in these 1D systems on the single-molecule junction transmission. Additionally, we discuss how the self-energy from the electrode-molecule coupling and the on-site energy of the edge sites can be tuned to create longer wires with reversed conductance decays.

Highly conducting single-molecule topological insulators based on mono- and di-radical cations.

Single-molecule topological insulators are promising candidates as conducting wires over nanometre length scales. A key advantage is their ability to exhibit quasi-metallic transport, in contrast to conjugated molecular wires which typically exhibit a low conductance that decays as the wire length increases. Here, we study a family of oligophenylene-bridged bis(triarylamines) with tunable and stable mono- or di-radicaloid character. These wires can undergo one- and two-electron chemical oxidations to the corresponding mono-cation and di-cation, respectively. We show that the oxidized wires exhibit reversed conductance decay with increasing length, consistent with the expectation for Su-Schrieffer-Heeger-type one-dimensional topological insulators. The 2.6-nm-long di-cation reported here displays a conductance greater than 0.1G0, where G0 is the conductance quantum, a factor of 5,400 greater than the neutral form. The observed conductance-length relationship is similar between the mono-cation and di-cation series. Density functional theory calculations elucidate how the frontier orbitals and delocalization of radicals facilitate the observed non-classical quasi-metallic behaviour.

Increased Molecular Conductance in Oligo[n]phenylene Wires by Thermally Enhanced Dihedral Planarization.

Coherent tunneling electron transport through molecular wires has been theoretically established as a temperature-independent process. Although several experimental studies have shown counter examples, robust models to describe this temperature dependence have not been thoroughly developed. Here, we demonstrate that dynamic molecular structures lead to temperature-dependent conductance within coherent tunneling regime. Using a custom-built variable-temperature scanning tunneling microscopy break-junction instrument, we find that oligo[n]phenylenes exhibit clear temperature-dependent conductance. Our calculations reveal that thermally activated dihedral rotations allow these molecular wires to have a higher probability of being in a planar conformation. As the tunneling occurs primarily through π-orbitals, enhanced coplanarization substantially increases the time-averaged tunneling probability. These calculations are consistent with the observation that more rotational pivot points in longer molecular wires leads to larger temperature-dependence on conductance. These findings reveal that molecular conductance within coherent and off-resonant electron transport regimes can be controlled by manipulating dynamic molecular structure.

π-Conjugated redox-active two-dimensional polymers as organic cathode materials.

Redox-active two-dimensional polymers (RA-2DPs) are promising lithium battery organic cathode materials due to their regular porosities and high chemical stabilities. However, weak electrical conductivities inherent to the non-conjugated molecular motifs used thus far limit device performance and the practical relevance of these materials. We herein address this problem by developing a modular approach to construct π-conjugated RA-2DPs with a new polycyclic aromatic redox-active building block PDI-DA. Efficient imine-condensation between PDI-DA and two polyfunctional amine nodes followed by quantitative alkyl chain removal produced RA-2DPs TAPPy-PDI and TAPB-PDI as conjugated, porous, polycrystalline networks. In-plane conjugation and permanent porosity endow these materials with high electrical conductivity and high ion diffusion rates. As such, both RA-2DPs function as organic cathode materials with good rate performance and excellent cycling stability. Importantly, the improved design enables higher areal mass-loadings than were previously available, which drives a practical demonstration of TAPPy-PDI as the power source for a series of LED lights. Collectively, this investigation discloses viable synthetic methodologies and design principles for the realization of high-performance organic cathode materials.

Theory of Chirality Induced Spin Selectivity: Progress and Challenges.

A critical overview of the theory of the chirality-induced spin selectivity (CISS) effect, that is, phenomena in which the chirality of molecular species imparts significant spin selectivity to various electron processes, is provided. Based on discussions in a recently held workshop, and further work published since, the status of CISS effects-in electron transmission, electron transport, and chemical reactions-is reviewed. For each, a detailed discussion of the state-of-the-art in theoretical understanding is provided and remaining challenges and research opportunities are identified.

Single-Molecule Junction Formation in Break-Junction Measurements.

The scanning tunneling microscope-based break-junction (STM-BJ) technique is the most common method used to study the electronic properties of single-molecule junctions. It relies on repeatedly forming and rupturing a Au contact in an environment of the target molecules. The probability of junction formation is typically very high (∼70-95%), prompting questions relating to how the nanoscale structure of the Au electrode before the metal point contact ruptures alters junction formation. Here we analyze conductance traces measured with the STM-BJ setup by combining correlation analysis and multiple machine learning tools, including gradient-boosted trees and neural networks. We show that two key features describing the Au-Au contact prior to rupture determine the extent of contact relaxation (snapback) and the probability of junction formation. Importantly, our data strongly indicate that molecular junctions are formed prior to the rupture of the Au-Au contact, explaining the high probability of junction formation observed in room-temperature solution measurements.

Destructive quantum interference in heterocyclic alkanes: the search for ultra-short molecular insulators.

Designing highly insulating sub-nanometer molecules is difficult because tunneling conductance increases exponentially with decreasing molecular length. This challenge is further enhanced by the fact that most molecules cannot achieve full conductance suppression with destructive quantum interference. Here, we present results for a series of small saturated heterocyclic alkanes where we show that conductance is suppressed due to destructive interference. Using the STM-BJ technique and density functional theory calculations, we confirm that their single-molecule junction conductance is lower than analogous alkanes of similar length. We rationalize the suppression of conductance in the junctions through analysis of the computed ballistic current density. We find there are highly symmetric ring currents, which reverse direction at the antiresonance in the Landauer transmission near the Fermi energy. This pattern has not been seen in earlier studies of larger bicyclic systems exhibiting interference effects and constitutes clear-cut evidence of destructive σ-interference. The finding of heterocyclic alkanes with destructive quantum interference charts a pathway for chemical design of short molecular insulators using organic molecules.