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Open-shell materials bearing multiple spin centres provide a key route to efficient charge transport in single-molecule electronic devices. They have narrow energy gaps, and their molecular orbitals align closely to the Fermi level of the metallic electrodes, thus allowing efficient electronic transport and higher conductance. Maintaining and stabilising multiple open-shell states-especially in contact with metallic electrodes-is however very challenging, generally requiring a continuous chemical or electrochemical potential to avoid self-immolation of the open-shell character. To overcome this issue, we designed, synthesised, and measured the conductance of a series of bis(indeno) fused acenes, where stability is imparted by a close-shell quinoidal conformation in resonance with the diradical electronic configuration. We show here that these compounds have anti-ohmic behaviour, with conductance increasing with increasing molecular length, at an unprecedented rate and across the entire bias window ( ± 1 . 3 V ${\pm 1.3\ V}$ ). Density Functional Theory (DFT) calculations support our findings, showing the rapidly narrowing HOMO-LUMO gap, unique to these diradicaloid structures, is responsible for the observed behaviour. Our results provide a framework for achieving efficient transport in neutral compounds and demonstrate the promise that diradicaloid materials have in single-molecule electronics, owing to their great stability and unique electronic structure., (© 2024 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

The metal-electrode interface is key to unlocking emergent behaviour in all organic electrified systems, from battery technology to molecular electronics. In the latter, interfacial engineering has enabled efficient transport, higher device stability, and novel functionality. Mechanoresistivity - the change in electrical behaviour in response to a mechanical stimulus and a pathway to extremely sensitive force sensors - is amongst the most studied phenomena in molecular electronics, and the molecule-electrode interface plays a pivotal role in its emergence, reproducibility, and magnitude. In this contribution, we show that organometallic molecular wires incorporating a Pt(II) cation show mechanoresistive behaviour of exceptional magnitude, with conductance modulations of more than three orders of magnitude upon compression by as little as 1 nm. We synthesised series of cyclometalated Pt(II) molecular wires, and used scanning tunnelling microscopy - break junction techniques to characterise their electromechanical behaviour. Mechanoresistivity arises from an interaction between the Pt(II) cation and the Au electrode triggered by mechanical compression of the single-molecule device, and theoretical modelling confirms this hypothesis. Our study provides a new tool for the design of functional molecular wires by exploiting previously unreported ion-metal interactions in single-molecule devices, and develops a new framework for the development of mechanoresistive molecular junctions., (© 2024 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

There are several binding groups used within molecular electronics for anchoring molecules to metal electrodes (e.g., R-SMe, R-NH 2 , R-CS 2 - , R-S - ). However, some anchoring groups that bind strongly to electrodes have poor/unknown stability, some have weak electrode coupling, while for some their binding motifs are not well defined. Further binding groups are required to aid molecular design and to achieve a suitable balance in performance across a range of properties. We present an in-depth investigation into the use of carbodithioate esters as contact groups for single-molecule conductance measurements, using scanning tunnelling microscopy break junction measurements (STM-BJ) and detailed surface spectroscopic analysis. We demonstrate that the methyl carbodithioate ester acts as an effective contact for gold electrodes in STM-BJ measurements. Surface enhanced Raman measurements demonstrate that the C=S functionality remains intact when adsorbed on to gold nanoparticles. A gold(I) complex was also synthesised showing a stable C=S→Au I interaction from the ester. Comparison with a benzyl thiomethyl ether demonstrates that the C=S moiety significantly contributes to charge transport in single-molecule junctions. The overall performance of the CS 2 Me group demonstrates it should be used more extensively and has strong potential for the fabrication of larger area devices with long-term stability., (© 2024 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

Mechanosensitive molecular junctions, where conductance is sensitive to an applied stress such as force or displacement, are a class of nanoelectromechanical systems unique for their ability to exploit quantum mechanical phenomena. Most studies so far relied on reconfiguration of the molecule-electrode interface to impart mechanosensitivity, but this approach is limited and, generally, poorly reproducible. Alternatively, devices that exploit conformational flexibility of molecular wires have been recently proposed. The mechanosensitive properties of molecular wires containing the 1,1'-dinaphthyl moiety are presented here. Rotation along the chemical bond between the two naphthyl units is possible, giving rise to two conformers (transoid and cisoid) that have distinctive transport properties. When assembled as single-molecule junctions, it is possible to mechanically trigger the transoid to cisoid transition, resulting in an exquisitely sensitive mechanical switch with high switching ratio (> 10 2 ). Theoretical modeling shows that charge reconfiguration upon transoid to cisoid transition is responsible for the observed behavior, with generation and subsequent lifting of quantum interference features. These findings expand the experimental toolbox of molecular electronics with a novel chemical structure with outstanding electromechanical properties, further demonstrating the importance of subtle changes in charge delocalization on the transport properties of single-molecule devices., (© 2024 The Authors. Small published by Wiley‐VCH GmbH.)

Existing modelling tools, developed to aid the design of efficient molecular wires and to better understand their charge-transport behaviour and mechanism, have limitations in accuracy and computational cost. Further research is required to develop faster and more precise methods that can yield information on how charge transport properties are impacted by changes in the chemical structure of a molecular wire. In this study, we report a clear semilogarithmic correlation between charge transport efficiency and nuclear magnetic resonance chemical shifts in multiple series of molecular wires, also accounting for the presence of chemical substituents. The NMR data was used to inform a simple tight-binding model that accurately captures the experimental single-molecule conductance values, especially useful in this case as more sophisticated density functional theory calculations fail due to inherent limitations. Our study demonstrates the potential of NMR spectroscopy as a valuable tool for characterising, rationalising, and gaining additional insights on the charge transport properties of single-molecule junctions., (© 2024 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

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., (© 2023 The Authors. Small published by Wiley-VCH GmbH.)

Controlling the orientation of complex molecules in molecular junctions is crucial to their development into functional devices. To date, this has been achieved through the use of multipodal compounds (i.e., containing more than two anchoring groups), resulting in the formation of tri/tetrapodal compounds. While such compounds have greatly improved orientation control, this comes at the cost of lower surface coverage. In this study, we examine an alternative approach for generating multimodal compounds by binding multiple independent molecular wires together through metal coordination to form a molecular bundle. This was achieved by coordinating iron(II) and cobalt(II) to 5,5'-bis(methylthio)-2,2'-bipyridine ( L 1 ) and (methylenebis(4,1-phenylene))bis(1-(5-(methylthio)pyridin-2-yl)methanimine) ( L 2 ) to give two monometallic complexes, Fe-1 and Co-1 , and two bimetallic helicates, Fe-2 and Co-2 . Using XPS, all of the complexes were shown to bind to a gold surface in a fac fashion through three thiomethyl groups. Using single-molecule conductance and DFT calculations, each of the ligands was shown to conduct as an independent wire with no impact from the rest of the complex. These results suggest that this is a useful approach for controlling the geometry of junction formation without altering the conductance behavior of the individual molecular wires.

The present work provides an insight into the effect of connectivity isomerization of metal-2,2'-bipyridine complexes. For that purpose, two new 2,2'-bipyridine (bpy) ligand systems, 4,4'-bis(4-(methylthio)phenyl)-2,2'-bipyridine (L meta ) and 5,5'-bis(3,3-dimethyl-2,3-dihydrobenzothiophen-5-yl)-2,2'-bipyridine (L para ) were synthesized and coordinated to rhenium and manganese to obtain the corresponding complexes MnL meta (CO) 3 Br, ReL meta (CO) 3 Br, MnL para (CO) 3 Br, MoL para (CO) 4 and ReL para (CO) 3 Br. The experimental and theoretical results revealed that coordination to the para system, i.e., the metal ion peripheral to the conductance path, gave a slightly increased conductance compared to the free ligand attributed to the reduced highest occupied molecular orbital (HOMO)-least unoccupied molecular orbital (LUMO) gap. The meta-based system formed a destructive quantum interference feature that reduced the conductance of a S···S contacted junction to below 10 -5.5 G o , reinforcing the importance of contact group connectivity for molecular wire conductance., Competing Interests: The authors declare no competing financial interest., (© 2023 The Authors. Published by American Chemical Society.)

The environment surrounding a molecular junction affects its charge-transport properties and, therefore, must be chosen with care. In the case of measurements in liquid media, the solvent must provide good solvation, grant junction stability, and, in the case of electrolyte gating experiments, allow efficient electrical coupling to the gate electrodes through control of the electrical double layer. We evaluated in this study the deep eutectic solvent mixture (DES) ethaline, which is a mixture of choline chloride and ethylene glycol (1:2), for single-molecule junction fabrication with break-junction techniques. In ethaline, we were able to (i) measure challenging and poorly soluble molecular wires, exploiting the improved solvation capabilities offered by DESs, and (ii) efficiently apply an electrostatic gate able to modulate the conductance of the junction by approximately an order of magnitude within a ∼1 V potential window. The electrochemical gating results on a Au- VDP -Au junction follow exceptionally well the single-level modeling with strong gate coupling (where VDP is 1,2-di(pyridine-4-yl)ethene). Ethaline is also an ideal solvent for the measurement of very short molecular junctions, as it grants a greatly reduced snapback distance of the metallic electrodes upon point-contact rupture. Our work demonstrates that DESs are viable alternatives to often relatively expensive ionic liquids, offering good versatility for single-molecule electrical measurements., Competing Interests: The authors declare no competing financial interest., (© 2023 The Authors. Published by American Chemical Society.)

Most studies in molecular electronics focus on altering the molecular wire backbone to tune the electrical properties of the whole junction. However, it is often overlooked that the chemical structure of the groups anchoring the molecule to the metallic electrodes influences the electronic structure of the whole system and, therefore, its conductance. We synthesised electron-accepting dithienophosphole oxide derivatives and fabricated their single-molecule junctions. We found that the anchor group has a dramatic effect on charge-transport efficiency: in our case, electron-deficient 4-pyridyl contacts suppress conductance, while electron-rich 4-thioanisole termini promote efficient transport. Our calculations show that this is due to minute changes in charge distribution, probed at the electrode interface. Our findings provide a framework for efficient molecular junction design, especially valuable for compounds with strong electron withdrawing/donating backbones., (© 2023 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

The electrical properties of large area molecular devices consisting of gold nanoparticles (GNPs) sandwiched between a double layer of alkanedithiol linkers have been examined. These devices have been fabricated by a facile bottom-up assembly in which an alkanedithiol monolayer is first self-assembled on an underlying gold substrate followed by nanoparticle adsorption and then finally assembly of the top alkanedithiol layer. These devices are then sandwiched between the bottom gold substrates and a top eGaIn probe contact and current-voltage ( I - V ) curves recorded. Devices have been fabricated with 1,5-pentanedithiol, 1,6-hexanedithiol, 1,8-octanedithiol and 1,10-decanedithiol linkers. In all cases the electrical conductance of the double SAM junctions with GNPs is higher than the corresponding and much thinner single alkanedithiol SAM. Competing models for this enhanced conductance are discussed and it is suggested to have a topological origin arising from how the devices assemble or structure during the fabrication, which gives more efficient cross device electron transport pathways without the GNPs producing short circuits.

This paper describes the syntheses of several functionalized dihydropyrene (DHP) molecular switches with different substitution patterns. Regioselective nucleophilic alkylation of a 5-substituted dimethyl isophthalate allowed the development of a workable synthetic protocol for the preparation of 2,7-alkyne-functionalized DHPs. Synthesis of DHPs with surface-anchoring groups in the 2,7- and 4,9-positions is described. The molecular structures of several intermediates and DHPs were elucidated by X-ray single-crystal diffraction. Molecular properties and switching capabilities of both types of DHPs were assessed by light irradiation experiments, spectroelectrochemistry, and cyclic voltammetry. Spectroelectrochemistry, in combination with density functional theory (DFT) calculations, shows reversible electrochemical switching from the DHP forms to the cyclophanediene (CPD) forms. Charge-transport behavior was assessed in single-molecule scanning tunneling microscope (STM) break junctions, combined with density functional theory-based quantum transport calculations. All DHPs with surface-contacting groups form stable molecular junctions. Experiments show that the molecular conductance depends on the substitution pattern of the DHP motif. The conductance was found to decrease with increasing applied bias.

Integrating radical (open-shell) species into non-cryogenic nanodevices is key to unlocking the potential of molecular electronics. While many efforts have been devoted to this issue, in the absence of a chemical/electrochemical potential the open-shell character is generally lost in contact with the metallic electrodes. Herein, single-molecule devices incorporating a 6-oxo-verdazyl persistent radical have been fabricated using break-junction techniques. The open-shell character is retained at room temperature, and electrochemical gating permits in situ reduction to a closed-shell anionic state in a single-molecule transistor configuration. Furthermore, electronically driven rectification arises from bias-dependent alignment of the open-shell resonances. The integration of radical character, transistor-like switching, and rectification in a single molecular component paves the way to further studies of the electronic, magnetic, and thermoelectric properties of open-shell species., (© 2022 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

The single-molecular conductance of a redox active viologen molecular bridge between Au|graphene electrodes has been studied in an electrochemical gating configuration in an ionic liquid medium. A clear "off-on-off" conductance switching behaviour has been achieved through gating of the redox state when the electrochemical potential is swept. The Au|viologen|graphene junctions show single-molecule conductance maxima centred close to the equilibrium redox potentials for both reduction steps. The peak conductance of Au|viologen|graphene junctions during the first reduction is significantly higher than that of previously measured Au|viologen|Au junctions. This shows that even though the central viologen moiety is not directly linked to the enclosing electrodes, substituting one gold contact for a graphene one nevertheless has a significant impact on junction conductance values. The experimental data was compared against two theoretical models, namely a phase coherent tunnelling and an incoherent "hopping" model. The former is a simple gating monoelectronic model within density functional theory (DFT) which discloses the charge state evolution of the molecule with electrode potential. The latter model is the collective Kuznetsov Ulstrup model for 2-step sequential charge transport through the redox centre in the adiabatic limit. The comparison of both models to the experimental data is discussed for the first time. This work opens perspectives for graphene-based molecular transistors with more effective gating and fundamental understanding of electrochemical electron transfer at the single molecular level.

Molecules capable of mediating charge transport over several nanometers with minimal decay in conductance have fundamental and technological implications. Polymethine cyanine dyes are fascinating molecular wires because up to a critical length, they have no bond-length alternation (BLA) and their electronic structure resembles a one-dimensional free-electron gas. Beyond this threshold, they undergo a symmetry-breaking Peierls transition, which increases the HOMO-LUMO gap. We have investigated cationic cyanines with central polymethine chains of 5-13 carbon atoms ( Cy3 + -Cy11 + ). The absorption spectra and crystal structures show that symmetry breaking is sensitive to the polarity of the medium and the size of the counterion. X-ray crystallography reveals that Cy9·PF 6 and Cy11·B(C 6 F 5 ) 4 are Peierls distorted, with high BLA at one end of the π-system, away from the partially delocalized positive charge. This pattern of BLA distribution resembles that of solitons in polyacetylene. The single-molecule conductance is essentially independent of molecular length for the polymethine salts of Cy3 + -Cy11 + with the large B(C 6 F 5 ) 4 - counterion, but with the PF 6 - counterion, the conductance decreases for the longer molecules, Cy7 + -Cy11 + , because this smaller anion polarizes the π-system, inducing a symmetry-breaking transition. At higher bias (0.9 V), the conductance of the shorter chains, Cy3 + -Cy7 + , increases with length (negative attenuation factor, β = -1.6 nm -1 ), but the conductance still drops in Cy9 + and Cy11 + with the small polarizing PF 6 - counteranion.

The most probable single-molecule conductance of each member of a series of 12 conjugated molecular wires, 6 of which contain either a ruthenium or platinum center centrally placed within the backbone, has been determined. The measurement of a small, positive Seebeck coefficient has established that transmission through these molecules takes place by tunneling through the tail of the HOMO resonance near the middle of the HOMO-LUMO gap in each case. Despite the general similarities in the molecular lengths and frontier-orbital compositions, experimental and computationally determined trends in molecular conductance values across this series cannot be satisfactorily explained in terms of commonly discussed "single-parameter" models of junction conductance. Rather, the trends in molecular conductance are better rationalized from consideration of the complete molecular junction, with conductance values well described by transport calculations carried out at the DFT level of theory, on the basis of the Landauer-Büttiker model.

Indium tin oxide (ITO) is an attractive substrate for single-molecule electronics since it is transparent while maintaining electrical conductivity. Although it has been used before as a contacting electrode in single-molecule electrical studies, these studies have been limited to the use of carboxylic acid terminal groups for binding molecular wires to the ITO substrates. There is thus the need to investigate other anchoring groups with potential for binding effectively to ITO. With this aim, we have investigated the single-molecule conductance of a series of eight tolane or "tolane-like" molecular wires with a variety of surface binding groups. We first used gold-molecule-gold junctions to identify promising targets for ITO selectivity. We then assessed the propensity and selectivity of carboxylic acid, cyanoacrylic acid, and pyridinium-squarate to bind to ITO and promote the formation of molecular heterojunctions. We found that pyridinium squarate zwitterions display excellent selectivity for binding to ITO over gold surfaces, with contact resistivity comparable to that of carboxylic acids. These single-molecule experiments are complemented by surface chemical characterization with X-ray photoelectron spectroscopy, quartz crystal microbalance, contact angle determination, and nanolithography using an atomic force miscroscope. Finally, we report the first density-functional theory calculations involving ITO electrodes to model charge transport through ITO-molecule-gold heterojunctions.

The ability to control the charge state of individual molecules wired in two-terminal single-molecule junctions is a key challenge in molecular electronics, particularly in relation to the development of molecular memory and other computational componentry. Here we demonstrate that single porphyrin molecular junctions can be reversibly charged and discharged at elevated biases under ambient conditions due to the presence of a localised molecular eigenstate close to the Fermi edge of the electrodes. In particular, we can observe long-lived charge-states with lifetimes upwards of 1-10 seconds after returning to low bias and large changes in conductance, in excess of 100-fold at low bias. Our theoretical analysis finds charge-state lifetimes within the same time range as the experiments. The ambient operation demonstrates that special conditions such as low temperatures or ultra-high vacuum are not essential to observe hysteresis and stable charged molecular junctions.

Stimuli-responsive molecular junctions, where the conductance can be altered by an external perturbation, are an important class of nanoelectronic devices. These have recently attracted interest as large effects can be introduced through exploitation of quantum phenomena. We show here that significant changes in conductance can be attained as a molecule is repeatedly compressed and relaxed, resulting in molecular folding along a flexible fragment and cycling between an anti and a syn conformation. Power spectral density analysis and DFT transport calculations show that through-space tunneling between two phenyl fragments is responsible for the conductance increase as the molecule is mechanically folded to the syn conformation. This phenomenon represents a novel class of mechanoresistive molecular devices, where the functional moiety is embedded in the conductive backbone and exploits intramolecular nonbonding interactions, in contrast to most studies where mechanoresistivity arises from changes in the molecule-electrode interface.

Hot carriers in plasmonic nanostructures, generated via plasmon decay, play key roles in applications such as photocatalysis and in photodetectors that circumvent bandgap limitations. However, direct experimental quantification of steady-state energy distributions of hot carriers in nanostructures has so far been lacking. We present transport measurements from single-molecule junctions, created by trapping suitably chosen single molecules between an ultrathin gold film supporting surface plasmon polaritons and a scanning probe tip, that can provide quantification of plasmonic hot-carrier distributions. Our results show that Landau damping is the dominant physical mechanism of hot-carrier generation in nanoscale systems with strong confinement. The technique developed in this work will enable quantification of plasmonic hot-carrier distributions in nanophotonic and plasmonic devices., (Copyright © 2020 The Authors, some rights reserved; exclusive licensee American Association for the Advancement of Science. No claim to original U.S. Government Works.)

Polyoxometalates have been proposed in the literature as nanoelectronic components, where they could offer key advantages with their structural versatility and rich electrochemistry. Apart from a few studies on their ensemble behaviour (as monolayers or thin films), this potential remains largely unexplored. We synthesised a pyridyl-capped Anderson-Evans polyoxometalate and used it to fabricate single-molecule junctions, using the organic termini to chemically "solder" a single cluster to two nanoelectrodes. Operating the device in an electrochemical environment allowed us to probe charge transport through different oxidation states of the polyoxometalate, and we report here an efficient three-state transistor behaviour. Conductance data fits a quantum tunnelling mechanism with different charge-transport probabilities through different charge states. Our results show the promise of polyoxometalates in nanoelectronics and give an insight on their single-entity electrochemical behaviour., (© 2020 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.)

As a small molecule possessing both strong H-bond donor and acceptor functions, 1H-imidazole can participate in extensive homo- or heteromolecular H-bonding networks. These properties are important in Nature, as imidazole moieties are incorporated in many biologically-relevant compounds. Imidazole also finds applications ranging from corrosion inhibition to fire retardants and photography. We have found a peculiar behaviour of imidazole during scanning tunnelling microscopy-break junction (STM-BJ) experiments, in which oligomeric chains connect the two electrodes and allow efficient charge transport. We attributed this behaviour to the formation of hydrogen-bonding networks, as no evidence of such behaviour was found in 1-methylimidazole (incapable of participating in intramolecular hydrogen bonding). The results are supported by DFT calculations, which confirmed our hypothesis. These findings pave the road to the use of hydrogen-bonding networks for the fabrication of dynamic junctions based on supramolecular interactions.

Single-molecule junctions that are sensitive to compression or elongation are an emerging class of nanoelectromechanical systems (NEMS). Although the molecule-electrode interface can be engineered to impart such functionality, most studies to date rely on poorly defined interactions. We focused on this issue by synthesizing molecular wires designed to have chemically defined hemilabile contacts based on (methylthio)thiophene moieties. We measured their conductance as a function of junction size and observed conductance changes of up to two orders of magnitude as junctions were compressed and stretched. Localised interactions between weakly coordinating thienyl sulfurs and the electrodes are responsible for the observed effect and allow reversible monodentate⇄bidentate contact transitions as the junction is modulated in size. We observed an up to ≈100-fold sensitivity boost of the (methylthio)thiophene-terminated molecular wire compared with its non-hemilabile (methylthio)benzene counterpart and demonstrate a previously unexplored application of hemilabile ligands to molecular electronics., (© 2019 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.)

A key area of activity in contemporary molecular electronics is the chemical control of conductance of molecular junctions and devices. Here we study and modify a range of pyrrolodipyridines (carbazole-like) molecular wires. We are able to change the electrical conductance and quantum interference patterns by chemically regulating the bridging nitrogen atom in the tricyclic ring system. A series of eight different N-substituted pyrrolodipyridines has been synthesized and subjected to single-molecule electrical characterization using an STM break junction. Correlations of these experimental data with theoretical calculations underline the importance of the pyrrolic nitrogen in facilitating conductance across the molecular bridge and controlling quantum interference. The large chemical modulation for the meta -connected series is not apparent for the para -series, showing the competition between (i) meta -connectivity quantum interference phenomena and (ii) the ability of the pyrrolic nitrogen to facilitate conductance, that can be modulated by chemical substitution.

Charge transport is strongly suppressed by destructive quantum interference (DQI) in meta-connected 1,1'-biphenyl-containing molecules, resulting in low electrical conductance. Surprisingly, we have found that DQI is almost entirely overcome by adding a bridging carbonyl, to yield a cross-conjugated fluorenone. This contrasts with other π-systems, such as para-connected anthraquinone, where cross-conjugation results in low conductance.

Cumulenes are sometimes described as "metallic" because an infinitely long cumulene would have the band structure of a metal. Herein, we report the single-molecule conductance of a series of cumulenes and cumulene analogues, where the number of consecutive C=C bonds in the core is n=1, 2, 3, and 5. The [n]cumulenes with n=3 and 5 have almost the same conductance, and they are both more conductive than the alkene (n=1). This is remarkable because molecular conductance normally falls exponentially with length. The conductance of the allene (n=2) is much lower, because of its twisted geometry. Computational simulations predict a similar trend to the experimental results and indicate that the low conductance of the allene is a general feature of [n]cumulenes where n is even. The lack of length dependence in the conductance of [3] and [5]cumulenes is attributed to the strong decrease in the HOMO-LUMO gap with increasing length., (© 2019 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.)

Interference features in the transmission spectra can dominate charge transport in metal-molecule-metal junctions when they occur close to the contact Fermi energy ( E F ). Here, we show that by forming a charge-transfer complex with tetracyanoethylene (TCNE) we can introduce new constructive interference features in the transmission profile of electron-rich, thiophene-based molecular wires that almost coincide with E F . Complexation can result in a large enhancement of junction conductance, with very efficient charge transport even at relatively large molecular lengths. For instance, we report a conductance of 10 -3 G 0 (∼78 nS) for the ∼2 nm long α-quaterthiophene:TCNE complex, almost two orders of magnitude higher than the conductance of the bare molecular wire. As the conductance of the complexes is remarkably independent of features such as the molecular backbone and the nature of the contacts to the electrodes, our results strongly suggest that the interference features are consistently pinned near to the Fermi energy of the metallic leads. Theoretical studies indicate that the semi-occupied nature of the charge-transfer orbital is not only important in giving rise to the latter effect, but also could result in spin-dependent transport for the charge-transfer complexes. These results therefore present a simple yet effective way to increase charge transport efficiency in long and poorly conductive molecular wires, with important repercussions in single-entity thermoelectronics and spintronics.

Vascular leakage, protein exudation, and edema formation are events commonly triggered by inflammation and facilitated by gaps that form between adjacent endothelial cells (ECs) of the vasculature. In such paracellular gap formation, the role of EC contraction is widely implicated, and even therapeutically targeted. However, related measurement approaches remain slow, tedious, and complex to perform. Here, we have developed a multiplexed, high-throughput screen to simultaneously quantify paracellular gaps, EC contractile forces, and to visualize F-actin stress fibers, and VE-cadherin. As proof-of-principle, we examined barrier-protective mechanisms of the Rho-associated kinase inhibitor, Y-27632, and the canonical agonist of the Tie2 receptor, Angiopoietin-1 (Angpt-1). Y-27632 reduced EC contraction and actin stress fiber formation, whereas Angpt-1 did not. Yet both agents reduced thrombin-, LPS-, and TNFα-induced paracellular gap formation. This unexpected result suggests that Angpt-1 can achieve barrier defense without reducing EC contraction, a mechanism that has not been previously described. This insight was enabled by the multiplex nature of the force-based platform. The high-throughput format we describe should accelerate both mechanistic studies and the screening of pharmacological modulators of endothelial barrier function.

A key goal in molecular electronics has been to find molecules that facilitate efficient charge transport over long distances. Normally, molecular wires become less conductive with increasing length. Here, we report a series of fused porphyrin oligomers for which the conductance increases substantially with length by >10-fold at a bias of 0.7 V. This exceptional behavior can be attributed to the rapid decrease of the HOMO-LUMO gap with the length of fused porphyrins. In contrast, for butadiyne-linked porphyrin oligomers with moderate inter-ring coupling, a normal conductance decrease with length is found for all bias voltages explored (±1 V), although the attenuation factor (β) decreases from ca. 2 nm -1 at low bias to <1 nm -1 at 0.9 V, highlighting that β is not an intrinsic molecular property. Further theoretical analysis using density functional theory underlines the role of intersite coupling and indicates that this large increase in conductance with length at increasing voltages can be generalized to other molecular oligomers.

In recent years, the use of non-metallic electrodes for the fabrication of single-molecule junctions has developed into an elegant way to impart new properties to nanodevices. Integration of molecular junctions in a semiconducting platform would also speed technological deployment, as it would take advantage of established industrial infrastructures. In a previous proof-of-concept paper, we used simple α,ω-dithiol self-assembled monolayers on a gallium arsenide (GaAs) substrate to fabricate molecular Schottky diodes with a STM. In the devices, we were also able to detect the contribution of a single-molecule to the overall charge transport. The prepared devices can also be used as photodiodes, as GaAs is a III-V direct bandgap (1.42 eV at room temperature) semiconductor, and it efficiently absorbs visible light to generate a photocurrent. In this contribution, we demonstrate that fine control can be exerted on the electrical behaviour of a metal-molecule-GaAs junction by systematically altering the nature of the molecular bridge, the type and doping density of the semiconductor and the light intensity and wavelength. Molecular orbital energy alignment dominates the charge transport properties, resulting in strongly rectifying junctions prepared with saturated bridges (e.g. alkanedithiols), with increasingly ohmic characteristics as the degree of saturation is reduced through the introduction of conjugated moieties. The effects we observed are local, and may be observed with electrodes of only a few tens of nanometres in size, hence paving the way to the use of semiconducting nanoelectrodes to probe molecular properties. Perspectives of these new developments for single molecule semiconductor electrochemistry are also discussed.

Controlling the orientation of molecular conductors on the electrode surfaces is a critical factor in the development of single-molecule conductors. In the current study, we used the scanning tunnelling microscopy-based break junction (STM-BJ) technique to explore 'bare-bones' tripodal molecular wires, employing different anchor groups (AGs) at the 'top' and 'bottom' of the tripod. The triarylphosphine tris(4-(methylthio)phenyl)phosphine and its corresponding phosphine sulfide showed only a single high conductance feature in the resulting 1- and 2-dimensional conductance histograms, whereas analogous molecules with fewer than three thiomethyl AGs did not show clear conductance features. Thus, by systematic molecular modifications and with the aid of supporting DFT calculations, the binding geometry, with respect to the surface, was elucidated., Competing Interests: The authors declare no competing financial interest., (This journal is © The Royal Society of Chemistry.)

Disordered coagulation contributes to death in sepsis and lacks effective treatments. Existing markers of disseminated intravascular coagulation (DIC) reflect its sequelae rather than its causes, delaying diagnosis and treatment. Here we show that disruption of the endothelial Tie2 axis is a sentinel event in septic DIC. Proteomics in septic DIC patients revealed a network involving inflammation and coagulation with the Tie2 antagonist, angiopoietin-2 (Angpt-2), occupying a central node. Angpt-2 was strongly associated with traditional DIC markers including platelet counts, yet more accurately predicted mortality in 2 large independent cohorts (combined N = 1,077). In endotoxemic mice, reduced Tie2 signaling preceded signs of overt DIC. During this early phase, intravital imaging of microvascular injury revealed excessive fibrin accumulation, a pattern remarkably mimicked by Tie2 deficiency even without inflammation. Conversely, Tie2 activation normalized prothrombotic responses by inhibiting endothelial tissue factor and phosphatidylserine exposure. Critically, Tie2 activation had no adverse effects on bleeding. These results mechanistically implicate Tie2 signaling as a central regulator of microvascular thrombus formation in septic DIC and indicate that circulating markers of the Tie2 axis could facilitate earlier diagnosis. Finally, interventions targeting Tie2 may normalize coagulation in inflammatory states while averting the bleeding risks of current DIC therapies.

One of the principal aims of single-molecule electronics is to create practical devices out of individual molecules. Such devices are expected to play a particularly important role as novel sensors thanks to their response to wide ranging external stimuli. Here we show that the conductance of a molecular junction can depend on two independent stimuli simultaneously. Using a scanning tunnelling microscope break-junction technique (STM-BJ), we found that the conductance of 4,4'-vinylenedipyridine (44VDP) molecular junctions with Ni contacts depends on both the electrochemically applied gate voltage and the pH of the environment. Hence, not only can the Ni|44VDP|Ni junction function as a pH-sensitive switch, but the value of the pH at which switching takes place can be tuned electrically. Furthermore, through the simultaneous control of pH and potential the STM-BJ technique delivers unique insight into the acid-base reaction, including the observation of discrete proton transfers to and from a single molecule.

If the factors controlling the decay in single-molecule electrical conductance G with molecular length L could be understood and controlled, then this would be a significant step forward in the design of high-conductance molecular wires. For a wide variety of molecules conducting by phase coherent tunnelling, conductance G decays with length following the relationship G = Ae -βL . It is widely accepted that the attenuation coefficient β is determined by the position of the Fermi energy of the electrodes relative to the energy of frontier orbitals of the molecular bridge, whereas the terminal anchor groups which bind to the molecule to the electrodes contribute to the pre-exponential factor A. We examine this premise for several series of molecules which contain a central conjugated moiety (phenyl, viologen or α-terthiophene) connected on either side to alkane chains of varying length, with each end terminated by thiol or thiomethyl anchor groups. In contrast with this expectation, we demonstrate both experimentally and theoretically that additional electronic states located on thiol anchor groups can significantly decrease the value of β, by giving rise to resonances close to E F through coupling to the bridge moiety. This interplay between the gateway states and their coupling to a central conjugated moiety in the molecular bridges creates a new design strategy for realising higher-transmission molecular wires by taking advantage of the electrode-molecule interface properties.

Stimulation of protease-activated receptor 1 (PAR1) on endothelium by activated protein C (APC) is protective in several animal models of disease, and APC has been used clinically in severe sepsis and wound healing. Clinical use of APC, however, is limited by its immunogenicity and its anticoagulant activity. We show that a class of small molecules termed "parmodulins" that act at the cytosolic face of PAR1 stimulates APC-like cytoprotective signaling in endothelium. Parmodulins block thrombin generation in response to inflammatory mediators and inhibit platelet accumulation on endothelium cultured under flow. Evaluation of the antithrombotic mechanism showed that parmodulins induce cytoprotective signaling through Gβγ, activating a PI3K/Akt pathway and eliciting a genetic program that includes suppression of NF-κB-mediated transcriptional activation and up-regulation of select cytoprotective transcripts. STC1 is among the up-regulated transcripts, and knockdown of stanniocalin-1 blocks the protective effects of both parmodulins and APC. Induction of this signaling pathway in vivo protects against thromboinflammatory injury in blood vessels. Small-molecule activation of endothelial cytoprotection through PAR1 represents an approach for treatment of thromboinflammatory disease and provides proof-of-principle for the strategy of targeting the cytoplasmic surface of GPCRs to achieve pathway selective signaling., Competing Interests: Conflict of interest statement: R.F. and C.D. are inventors on a patent describing parmodulins.

We have employed the scanning tunneling microscope break-junction technique to investigate the single-molecule conductance of a family of 5,15-diaryl porphyrins bearing thioacetyl (SAc) or methylsulfide (SMe) binding groups at the ortho position of the phenyl rings (S2 compounds). These ortho substituents lead to two atropisomers, cis and trans, for each compound, which do not interconvert in solution under ambient conditions; even at high temperatures, isomerization takes several hours (half-life 15 h at 140 °C for SAc in C 2 Cl 4 D 2 ). All the S2 compounds exhibit two conductance groups, and comparison with a monothiolated (S1) compound shows the higher group arises from a direct Au-porphyrin interaction. The lower conductance group is associated with the S-to-S pathway. When the binding group is SMe, the difference in junction length distribution reflects the difference in S-S distance (0.3 nm) between the two isomers. In the case of SAc, there are no significant differences between the plateau length distributions of the two isomers, and both show maximal stretching distances well exceeding their calculated junction lengths. Contact deformation accounts for part of the extra length, but the results indicate that cis-to-trans conversion takes place in the junction for the cis isomer. The barrier to atropisomerization is lower than the strength of the thiolate Au-S and Au-Au bonds, but higher than that of the Au-SMe bond, which explains why the strain in the junction only induces isomerization in the SAc compound.