Search

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.)

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.)

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.)

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.)

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.)

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.)

A key target in molecular electronics has been molecules having switchable electrical properties. Switching between two electrical states has been demonstrated using such stimuli as light, electrochemical voltage, complexation and mechanical modulation. A classic example of the latter is the switching of 4,4'-bipyridine, leading to conductance modulation of around 1 order of magnitude. Here, we describe the use of side-group chemistry to control the properties of a single-molecule electromechanical switch, which can be cycled between two conductance states by repeated compression and elongation. While bulky alkyl substituents inhibit the switching behavior, π-conjugated side-groups reinstate it. DFT calculations show that weak interactions between aryl moieties and the metallic electrodes are responsible for the observed phenomenon. This represents a significant expansion of the single-molecule electronics "tool-box" for the design of junctions with electromechanical properties., (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The compounds and complexes 1,4-C 6 H 4 (C≡C-cyclo-3-C 4 H 3 S) 2 (2), trans-[Pt(C≡C-cyclo-3-C 4 H 3 S) 2 (PEt 3 ) 2 ] (3), trans-[Ru(C≡C-cyclo-3-C 4 H 3 S) 2 (dppe) 2 ] (4; dppe=1,2-bis(diphenylphosphino)ethane) and trans-[Ru(C≡C-cyclo-3-C 4 H 3 S) 2 {P(OEt) 3 } 4 ] (5) featuring the 3-thienyl moiety as a surface contacting group for gold electrodes have been prepared, crystallographically characterised in the case of 3-5 and studied in metal|molecule|metal junctions by using both scanning tunnelling microscope break-junction (STM-BJ) and STM-I(s) methods (measuring the tunnelling current (I) as a function of distance (s)). The compounds exhibit similar conductance profiles, with a low conductance feature being more readily identified by STM-I(s) methods, and a higher feature by the STM-BJ method. The lower conductance feature was further characterised by analysis using an unsupervised, automated multi-parameter vector classification (MPVC) of the conductance traces. The combination of similarly structured HOMOs and non-resonant tunnelling mechanism accounts for the remarkably similar conductance values across the chemically distinct members of the family 2-5., (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The preparation, characterization and electrical properties of Langmuir-Blodgett (LB) films composed of a symmetrically substituted oligomeric phenylene ethynylene derivative, namely, 4,4'-[1,4-phenylenebis(ethyne-2,1-diyl)]dibenzoic acid (OPE2A), are described. Analysis of the surface pressure versus area per molecule isotherms and Brewster angle microscopy reveal that good-quality Langmuir (L) films can be formed both on pure water and a basic subphase. Monolayer L films were transferred onto solid substrates with a transfer ratio of unity to obtain LB films. Both L and LB films prepared on or from a pure water subphase show a red shift in the UV/Vis spectrum of about 14 nm, in contrast to L and LB films prepared from a basic subphase, which show a hypsochromic shift of 15 nm. This result, together with X-ray photoelectron spectroscopic and quartz crystal microbalance experiments, conclusively demonstrate formation of one-layer LB films in which OPE2A molecules are chemisorbed onto gold substrates and consequently -COO-Au junctions are formed. In LB films prepared on a basic subphase the other terminal acid group is also deprotonated and associates with an Na(+) counterion. In contrast, LB films prepared from a pure water subphase preserve the protonated acid group, and lateral H-bonds with neighbouring molecules give rise to a supramolecular structure. STM-based conductance studies revealed that films prepared from a basic subphase are more conductive than the analogous films prepared from pure water, and the electrical conductance of the deprotonated films also coincides more closely with single-molecule conductance measurements. This result was interpreted not only in terms of better electron transmission in -COO-Au molecular junctions, but also in terms of the presence of lateral H-bonds in the films formed from pure water, which lead to reduced conductance of the molecular junctions., (Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The length dependence of charge transport is evaluated in three families of porphyrin-based wires. Planar edge-fused tapes and alkyne-linked oligomers mediate efficient charge transport with exceptionally shallow distance dependence, whereas the conductances of the twisted singly linked chains decrease steeply with increasing oligomer length. The planar tapes are more conjugated than the alkyne-linked oligomers, but these two types of wires have similar conductance attenuation factors., (Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)