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Electrografting of an oligophenylene ethynylene monolayer (OPEH) onto a Mylar®-supported PEDOT : PSS and graphene substrate prior to wet-transfer of a graphene top-electrode has been used to create flexible and transparent large-area Mylar–PEDOT : PSS|OPEH|Graphene molecular junctions. The electrical conductance of the Mylar–PEDOT : PSS|OPEH|Graphene structure was determined by conductive probe atomic force microscopy (c-AFM), sampling various regions across the surfaces of multiple devices. All registered I–V curves (sampling size ∼150 tests) give a sigmoidal response, consistent with through molecule conductance and ruling out the presence of direct electrode contacts or short-circuits. The demonstration of the combined use of Mylar-supported PEDOT : PSS and graphene as alternative electrode materials to conventional metal thin film electrodes in large-area molecular junctions opens avenues to enable flexible and transparent molecular (opto)electronic devices.

As part of on-going efforts to optimize the electrical performance and stability of molecular electronic components, anchor groups that bind molecules to electrode surfaces via multiple points of connection (multipodal contacts) have begun to attract attention. Here an oligo(arylene)ethynylene (OAE) derivative with ‘tripodal’ 2,6-bis((methylthio)methyl)pyridine anchoring groups at both molecular termini has been prepared and used to form well-ordered monolayer Langmuir films at the air–water interface. These films were transferred onto solid supports (surface pressure of transference 8 mN m−1) to give homogeneous, densely packed, monolayer Langmuir–Blodgett (LB) films, which efficiently block a gold electrode surface. Within the surface-supported LB film, the molecules are oriented with a tilt angle of approximately 30° to the surface normal and contacted through both the ‘buttressed’ methylthioether groups and the pyridine nitrogen atom, as determined by X-ray photoelectron spectroscopy (XPS) and shell-isolated nanoparticle-enhanced Raman spectroscopy (SHINERS). Molecular junctions formed by contact of a single molecule within the film by the “STM touch-to-contact” method give a most probable molecular conductance of 4.4 × 10−5G0. This value compares well with the single molecule conductance of 1,4-bis(pyridin-4-ylethynyl)benzene determined by a variety of methods (3.2–5.4 × 10−5G0), indicating that the addition of the buttressing groups does not perturb the favourable electrical characteristics of the pyridyl contacting group. Consistent with these conductance data, a transition voltage (Vtrans = 0.48 V) was observed for this ‘buttressed’, pyridine-contacted OAE derivative, indicating relatively good alignment of the metal electrode Fermi level and the frontier molecular orbitals.

The compounds and complexes 1,4-CH(C≡C-cyclo-3-CHS) (2), trans-[Pt(C≡C-cyclo-3-CHS)(PEt)] (3), trans-[Ru(C≡C-cyclo-3-CHS)(dppe)] (4; dppe=1,2-bis(diphenylphosphino)ethane) and trans-[Ru(C≡C-cyclo-3-CHS){P(OEt)}] (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.

Nanoscience and nanotechnology have reached the syllabi of many upper-division undergraduate and master-level courses all over the world. There is therefore a growing need for practical exercises that illustrate the fabrication, characterization, properties, and applications of nanomaterials. Here we describe an advanced-level laboratory experiment in which students had the opportunity to fabricate surfaces modified by ordered monolayers and nanostructured materials. The surface modification was quantified by means of a quartz crystal microbalance, while the electrochemical properties of the nanoarchitectures were assessed using cyclic voltammetry experiments. Electron transfer across self-assembled monolayers mediated by gold nanoparticles was presented as a topic for discussion, and consideration of potential practical applications of the observed phenomena (catalytic and electrocatalytic processes, as well as development of optical, (opto)electronic, and photovoltaic devices with enhanced properties) was proposed as a further reading exercise.

A detailed study of the trimethylsilylethynyl moiety, –C[triple bond]CSiMe3 (TMSE) , as an anchoring group in metalmoleculemetal junctions, using a combination of experiment and density functional theory is presented. It is shown that the TMSE anchoring group provides improved control over the molecule-substrate arrangement within metalmoleculemetal junctions, with the steric bulk of the methyl groups limiting the number of highly transmissive binding sites at the electrode surface, resulting in a single sharp peak in the conductance histograms recorded by both the in situ break junction and I(s) STM techniques. As a consequence of the low accessibility of the TMSE group to surface binding configurations of measurable conductance, only about 10% of gold break junction formation cycles result in the clear formation of molecular junctions in the experimental histograms. The DFT-computed transmission characteristics of junctions formed from the TMSE-contacted oligo(phenylene)ethynylene (OPE)-based molecules described here are dominated by tunneling effects through the highest-occupied molecular orbitals (HOMOs). This gives rise to similar conductance characteristics in these TMSE-contacted systems as found in low conductance-type junctions based on comparably structured OPE-derivatives with amine-contacts that also conduct through HOMO-based channels.

Monolayer Langmuir–Blodgett (LB) films of 1,4-bis(pyridin-4-ylethynyl)benzene (1) together with the “STM touch-to-contact” method have been used to study the nature of metal–monolayer–metal junctions in which the pyridyl group provides the contact at both molecule–surface interfaces. Surface pressure vs area per molecule isotherms and Brewster angle microscopy images indicate that 1 forms true monolayers at the air–water interface. LB films of 1 were fabricated by deposition of the Langmuir films onto solid supports resulting in monolayers with surface coverage of 0.98 × 10−9 mol·cm−2. The morphology of the LB films that incorporate compound 1 was studied using atomic force microscopy (AFM). AFM images indicate the formation of homogeneous, monomolecular films at a surface pressure of transference of 16 mN·m−1. The UV–vis spectra of the Langmuir and LB films reveal that 1 forms two dimensional J-aggregates. Scanning tunneling microscopy (STM), in particular the “STM touch-to-contact” method, was used to determine the electrical properties of LB films of 1. From these STM studies symmetrical I–V curves were obtained. A junction conductance of 5.17 × 10−5 G 0 results from the analysis of the pseudolinear (ohmic) region of the I–V curves. This value is higher than that of the conductance values of LB films of phenylene-ethynylene derivatives contacted by amines, thiols, carboxylate, trimethylsilylethynyl or acetylide groups. In addition, the single molecule I–V curve of 1 determined using the I(s) method is in good agreement with the I–V curve obtained for the LB film, and both curves fit well with the Simmons model. Together, these results not only indicate that the mechanism of transport through these metal–molecule–metal junctions is non-resonant tunneling, but that lateral interactions between molecules within the LB film do not strongly influence the molecule conductance. The results presented here complement earlier studies of single molecule conductance of 1 usi