Planar aromatic anchors control the electrical conductance of gold|molecule|graphene junctions.

The synthesis of a family of alkanethiol molecules with planar aromatic head groups, designed to anchor molecules effectively to graphene electrodes, is reported. Characterisation of self-assembled monolayers of these molecules on a gold surface via conductive atomic force microscopy shows that when an aromatic head group is present, the conductance G graphene obtained using a graphene coated probe is higher than the conductance G Pt obtained using a platinum (Pt) probe. For Pt probe and graphene probe junctions, the tunnelling decay constant of benzyl ether derivatives with an alkanethiol molecular backbone is determined as ß = 5.6 nm-1 and 3.5 nm-1, respectively. The conductance ratio G graphene/G Pt increases as the number of rings present in the aromatic head unit, n, increases. However, as the number of rings increases, the conductance path length increases because the planar head groups lie at an angle to the plane of the electrodes. This means that overall conductance decreases as n increases. Density functional theory-based charge transport calculations support these experimental findings. This study confirms that planar aromatic head groups can function as effective anchoring units for graphene electrodes in large area molecular junctions. However, the results also indicate that the size and geometry of these head groups must be considered in order to produce effective molecular designs.

Electrostatic Fermi level tuning in large-scale self-assembled monolayers of oligo(phenylene-ethynylene) derivatives.

Understanding and controlling the orbital alignment of molecules placed between electrodes is essential in the design of practically-applicable molecular and nanoscale electronic devices. The orbital alignment is highly determined by the molecule-electrode interface. Dependence of orbital alignment on the molecular anchor group for single molecular junctions has been intensively studied; however, when scaling-up single molecules to large parallel molecular arrays (like self-assembled monolayers (SAMs)), two challenges need to be addressed: 1. Most desired anchor groups do not form high quality SAMs. 2. It is much harder to tune the frontier molecular orbitals via a gate voltage in SAM junctions than in single molecular junctions. In this work, we studied the effect of the molecule-electrode interface in SAMs with a micro-pore device, using a recently developed tetrapodal anchor to overcome challenge 1, and the combination of a single layered graphene top electrode with an ionic liquid gate to solve challenge 2. The zero-bias orbital alignment of different molecules was signalled by a shift in conductance minimum vs. gate voltage for molecules with different anchoring groups. Molecules with the same backbone, but a different molecule-electrode interface, were shown experimentally to have conductances that differ by a factor of 5 near zero bias. Theoretical calculations using density functional theory support the trends observed in the experimental data. This work sheds light on how to control electron transport within the HOMO-LUMO energy gap in molecular junctions and will be applicable in scaling up molecular electronic systems for future device applications.

Heteroatom Effects on Quantum Interference in Molecular Junctions: Modulating Antiresonances by Molecular Design.

Controlling charge transport through molecular wires by utilizing quantum interference (QI) is a growing topic in single-molecular electronics. In this article, scanning tunneling microscopy-break junction techniques and density functional theory calculations are employed to investigate the single-molecule conductance properties of four molecules that have been specifically designed to test extended curly arrow rules (ECARs) for predicting QI in molecular junctions. Specifically, for two new isomeric 1-phenylpyrrole derivatives, the conductance pathway between the gold electrodes must pass through a nitrogen atom: this novel feature is designed to maximize the influence of the heteroatom on conductance properties and has not been the subject of prior investigations of QI. It is shown, experimentally and computationally, that the presence of a nitrogen atom in the conductance pathway increases the effect of changing the position of the anchoring group on the phenyl ring from para to meta, in comparison with biphenyl analogues. This effect is explained in terms of destructive QI (DQI) for the meta-connected pyrrole and shifted DQI for the para-connected isomer. These results demonstrate modulation of antiresonances by molecular design and verify the validity of ECARs as a simple "pen-and-paper" method for predicting QI behavior. The principles offer new fundamental insights into structure-property relationships in molecular junctions and can now be exploited in a range of different heterocycles for molecular electronic applications, such as switches based on external gating, or in thermoelectric devices.

A review of oligo(arylene ethynylene) derivatives in molecular junctions.

Oligo(arylene ethynylene) (OAE) derivatives are the "workhorse" molecules of molecular electronics. Their ease of synthesis and flexibility of functionalisation mean that a diverse array of OAE molecular wires have been designed, synthesised and studied theoretically and experimentally in molecular junctions using both single-molecule and ensemble methods. This review summarises the breadth of molecular designs that have been investigated with emphasis on structure-property relationships with respect to the electronic conductance of OAEs. The factors considered include molecular length, connectivity, conjugation, (anti)aromaticity, heteroatom effects and quantum interference (QI). Growing interest in the thermoelectric properties of OAE derivatives, which are expected to be at the forefront of research into organic thermoelectric devices, is also explored.

Extended curly arrow rules to rationalise and predict structural effects on quantum interference in molecular junctions.

The ability to easily and reliably predict quantum interference (QI) behaviour would facilitate the design of functional molecular wires with potential applications in switches, transistors and thermoelectric devices. A variety of predictive methods exist, but with the exception of computationally-expensive DFT-based charge transport simulations, these often fail to account for the experimentally observed behaviour of molecules that differ significantly in structure from alternant polycyclic aromatic hydrocarbons. By considering a range of prior studies we have developed an extension to predictive "curly arrow rules". We show that, in most cases, these extended curly arrow rules (ECARs) can rationalise the type of QI exhibited by conjugated molecular wires containing heteroatoms, cross-conjugation and/or non-alternant structures. ECARs provide a straightforward "pen-and-paper" method to predict whether a molecular wire will display constructive, destructive or "shifted destructive" QI, i.e. whether or not its transmission function would be expected to show an antiresonance, and if this antiresonance would occur close to the Fermi energy or be shifted elsewhere.

Unusual dual-emissive heteroleptic iridium complexes incorporating TADF cyclometalating ligands.

Five new neutral heteroleptic iridium(iii) complexes IrL2(pic) (2-6) based on the archetypical blue emitter FIrpic have been synthesised. The cyclometallating ligands L are derived from 2-(2,6-F2-3-pyridyl)-4-mesitylpyridine (7), 2-(3-cyano-2,6-F2-phenyl)-4-mesitylpyridine (8), 2-(2,6-F2-phenyl)-4-[2,7-(HexO)2-9H-carbazol-9-yl]pyridine (9), 2-(2,6-F2-3-pyridyl)-4-[2,7-(HexO)2-9H-carbazol-9-yl]pyridine (10) and 2-(3-cyano-2,6-F2-phenyl)-4-[2,7-(HexO)2-9H-carbazol-9-yl]pyridine (11) for complexes 2, 3, 4, 5 and 6, respectively. The carbazole-functionalised ligands 9-11 show weak thermally activated delayed fluorescence (TADF) in solution. Complexes 5 and 6 reveal dual emission in polar solvents. A broad charge transfer (CT) band appears and increases in intensity relative to the higher energy emission band as solvent polarity is increased. The dual emission occurs when the energy of the ligand 3CT state is comparable to that of the 3MLCT state of the complex, resulting in fast interconversion between the two. Assignment of the ligand TADF and dual emission properties is supported by hybrid density functional theory (DFT) and time dependent DFT (TD-DFT) calculations. Phosphorescent organic light emitting devices (PhOLEDs) have been fabricated using these complexes as sky-blue emitters, and their performance is compared to devices using FIrpic and the previously reported complex IrL2(pic) 1 (L from the 2-(2,6-F2-phenyl)-4-mesitylpyridine ligand). For identical device structures, the device containing the carbazole complex 4 performs best out of the seven complexes. The dual emission observed in solution for complexes 5 and 6 is not observed in their devices.

Carbazole-Based Tetrapodal Anchor Groups for Gold Surfaces: Synthesis and Conductance Properties.

As the field of molecular-scale electronics matures and the prospect of devices incorporating molecular wires becomes more feasible, it is necessary to progress from the simple anchor groups used in fundamental conductance studies to more elaborate anchors designed with device stability in mind. This study presents a series of oligo(phenylene-ethynylene) wires with one tetrapodal anchor and a phenyl or pyridyl head group. The new anchors are designed to bind strongly to gold surfaces without disrupting the conductance pathway of the wires. Conductive probe atomic force microscopy (cAFM) was used to determine the conductance of self-assembled monolayers (SAMs) of the wires in Au-SAM-Pt and Au-SAM-graphene junctions, from which the conductance per molecule was derived. For tolane-type wires, mean conductances per molecule of up to 10-4.37  G0 (Pt) and 10-3.78  G0 (graphene) were measured, despite limited electronic coupling to the Au electrode, demonstrating the potential of this approach. Computational studies of the surface binding geometry and transport properties rationalise and support the experimental results.

Salts accelerate the switching kinetics of a cyclobis(paraquat-p-phenylene) [2]rotaxane.

The rate at which the macrocyclic cyclobis(paraquat-p-phenylene) ring of a bistable [2]rotaxane moves from a tetrathiafulvalene station to an oxyphenylene station upon oxidation of the tetrathiafulvalene station is found to be increased in the presence of added salts. Compared to the salt-free case, 0.1 M solutions of a series of tetraalkylammonium hexafluorophosphate salts (R4N·PF6, R = H, Me, Et or n-Bu) and of tetrabutylammonium perchlorate (n-Bu4N·ClO4) all afford an increased switching rate, which is largest in the case of n-Bu4N·ClO4 with smaller anions. Variation in the size of the ammonium cation has no significant effect. These results indicate that the addition of excess ions can be used as an accelerator to speed up shuttling processes in rotaxanes and catenanes based on the mobile cyclobis(paraquat-p-phenylene) ring, and that the choice of anion offers a convenient means of controlling the extent of this effect.

Electrochemical control of the single molecule conductance of a conjugated bis(pyrrolo)tetrathiafulvalene based molecular switch.

As the field of unimolecular electronics develops, there is growing interest in the development of functionalised molecular wires, such as switches, which will allow for more complex molecular-scale circuits. To this end, a three redox state single molecule switch, 1, based on bis(pyrrolo)tetrathiafulvalene (BPTTF) has been designed, synthesised and investigated using scanning tunnelling microscopy break junction (STM-BJ) studies and quantum transport calculations. Oxidising the BPTTF unit increases its conjugation, which was anticipated to increase the molecular conductance of 1. By changing the redox state of 1 electrochemically it was possible to vary the single molecule conductance by more than an order of magnitude (from 10-5.2G0 to 10-3.8G0). Simulations afforded a qualitatively similar trend. An additional, higher conductance feature is present in most traces at junction sizes of around 2.0 nm - further extension affords the switchable lower conductance feature at junction sizes closer to the molecular length (ca. 3.0 nm). Analysis of the conductance traces shows that these two conductance features occur sequentially in nearly all junctions. This behaviour is attributed to an alternative initial junction conformation in which one or more of the BPTTF sulfur atoms acts as an anchoring group. This hypothesis is supported by a computational study of binding conformations and STM-BJ studies on a model compound, 2, with only one thiol anchor. Our results indicate that the redox properties of BPTTF make it an excellent candidate for use in single molecule switches.

Formation of Two-Dimensional Micelles on Graphene: Multi-Scale Theoretical and Experimental Study.

Graphene and related two-dimensional (2D) materials possess outstanding electronic and mechanical properties, chemical stability, and high surface area. However, to realize graphene's potential for a range of applications in materials science and nanotechnology there is a need to understand and control the interaction of graphene with tailored high-performance surfactants designed to facilitate the preparation, manipulation, and functionalization of new graphene systems. Here we report a combined experimental and theoretical study of the surface structure and dynamics on graphene of pyrene-oligoethylene glycol (OEG) -based surfactants, which have previously been shown to disperse carbon nanotubes in water. Molecular self-assembly of the surfactants on graphitic surfaces is experimentally monitored and optimized using a graphene coated quartz crystal microbalance in ambient and vacuum environments. Real-space nanoscale resolution nanomechanical and topographical mapping of submonolayer surfactant coverage, using ultrasonic and atomic force microscopies both in ambient and ultrahigh vacuum, reveals complex, multilength-scale self-assembled structures. Molecular dynamics simulations show that at the nanoscale these structures, on atomically flat graphitic surfaces, are dependent upon the surfactant OEG chain length and are predicted to display a previously unseen class of 2D self-arranged "starfish" micelles (2DSMs). While three-dimensional micelles are well-known for their widespread uses ranging from microreactors to drug-delivery vehicles, these 2DSMs possess the highly desirable and tunable characteristics of high surface affinity coupled with unimpeded mobility, opening up strategies for processing and functionalizing 2D materials.

Advances in the synthesis of functionalised pyrrolotetrathiafulvalenes.

The electron-donor and unique redox properties of the tetrathiafulvalene (TTF, 1) moiety have led to diverse applications in many areas of chemistry. Monopyrrolotetrathiafulvalenes (MPTTFs, 4) and bispyrrolotetrathiafulvalenes (BPTTFs, 5) are useful structural motifs and have found widespread use in fields such as supramolecular chemistry and molecular electronics. Protocols enabling the synthesis of functionalised MPTTFs and BPTTFs are therefore of broad interest. Herein, we present the synthesis of a range of functionalised MPTTF and BPTTF species. Firstly, the large-scale preparation of the precursor species N-tosyl-(1,3)-dithiolo[4,5-c]pyrrole-2-one (6) is described, as well as the synthesis of the analogue N-tosyl-4,6-dimethyl-(1,3)-dithiolo[4,5-c]pyrrole-2-one (7). Thereafter, we show how 6 and 7 can be used to prepare BPTTFs using homocoupling reactions and functionalised MPTTFs using cross-coupling reactions with a variety of 1,3-dithiole-2-thiones (19). Subsequently, the incorporation of more complex functionality is discussed. We show how the 2-cyanoethyl protecting group can be used to afford MPTTFs functionalised with thioethers, exemplified by a series of ethylene glycol derivatives. Additionally, the merits of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) as an alternative to the most common deprotecting agent, CsOH·H2O are discussed. Finally, we show how a copper-mediated Ullman-type reaction can be applied to the N-arylation of MPTTFs and BPTTFs using a variety of aryl halides.

Reversible thermal switching of aqueous dispersibility of multiwalled carbon nanotubes.

Easily reversible aqueous dispersion/precipitation of multiwalled carbon nanotubes (MWNTs) has been demonstrated using small-molecule non-ionic pyrene-based surfactants, which exhibit lower critical solution temperature (LCST) phase behaviour. The MWNTs are dispersed by means of non-covalent interactions. The dispersibility can be switched "off" (i.e., MWNTs precipitated) upon heating and switched "on" (i.e., MWNTs re-dispersed) upon cooling and merely swirling the sample at room temperature, that is, under very mild conditions. This effect is also observed under high ionic strength conditions with NaCl in the aqueous phase.