The synthesis of functionalised diaryltetraynes and their transport properties in single-molecule junctions.

The synthesis and characterisation is described of six diaryltetrayne derivatives [Ar-(C≡C)4-Ar] with Ar=4-NO2-C6H4- (NO24), 4-NH(Me)C6H4- (NHMe4), 4-NMe2C6H4- (NMe24), 4-NH2-(2,6-dimethyl)C6H4- (DMeNH24), 5-indolyl (IN4) and 5-benzothienyl (BTh4). X-ray molecular structures are reported for NO24, NHMe4, DMeNH24, IN4 and BTh4. The stability of the tetraynes has been assessed under ambient laboratory conditions (20 °C, daylight and in air): NO24 and BTh4 are stable for at least six months without observable decomposition, whereas NHMe4, NMe24, DMeNH24 and IN4 decompose within a few hours or days. The derivative DMeNH24, with ortho-methyl groups partially shielding the tetrayne backbone, is considerably more stable than the parent compound with Ar=4-NH2C6H4 (NH24). The ability of the stable tetraynes to anchor in Au|molecule|Au junctions is reported. Scanning-tunnelling-microscopy break junction (STM-BJ) and mechanically controllable break junction (MCBJ) techniques are employed to investigate single-molecule conductance characteristics.

Harvesting UV photons for solar energy conversion applications.

We report the synthesis and characterization of five new donor­π­spacer­acceptor dye molecules with a diphenylamine donor, fluorene­1,2,5-oxadiazole spacers and a range of acceptor/anchor groups (carboxylic acid 1, cyanoacrylic acid 2 and 3, alcohol 4 and cyano 5) to facilitate electron injection from the excited dye into the TiO2 photoanode in dye-sensitized solar cells (DSSCs). Detailed photophysical studies have probed the dyes' excited state properties and revealed structure­property relationships within the series. Density functional theory (DFT) and time dependent DFT (TDDFT) calculations provide further insights into how the molecular geometry and electronic properties impact on the photovoltaic performance. A special feature of these dyes is that their absorption features are located predominantly in the UV region, which means the dye-sensitized TiO2 is essentially colorless. Nevertheless, DSSCs assembled from 1 and 2 exhibit photovoltaic power conversion efficiencies of η = 1.3 and 2.2%, respectively, which makes the dyes viable candidates for low-power solar cells that need to be transparent and colorless and for applications that require enhanced harvesting of UV photons.

Single-molecule conductance of functionalized oligoynes: length dependence and junction evolution.

We report a combined experimental and theoretical investigation of the length dependence and anchor group dependence of the electrical conductance of a series of oligoyne molecular wires in single-molecule junctions with gold contacts. Experimentally, we focus on the synthesis and properties of diaryloligoynes with n = 1, 2, and 4 triple bonds and the anchor dihydrobenzo[b]thiophene (BT). For comparison, we also explored the aurophilic anchor group cyano (CN), amino (NH2), thiol (SH), and 4-pyridyl (PY). Scanning tunneling microscopy break junction (STM-BJ) and mechanically controllable break junction (MCBJ) techniques are employed to investigate single-molecule conductance characteristics. The BT moiety is superior as compared to traditional anchoring groups investigated so far. BT-terminated oligoynes display a 100% probability of junction formation and possess conductance values which are the highest of the oligoynes studied and, moreover, are higher than other conjugated molecular wires of similar length. Density functional theory (DFT)-based calculations are reported for oligoynes with n = 1-4 triple bonds. Complete conductance traces and conductance distributions are computed for each family of molecules. The sliding of the anchor groups leads to oscillations in both the electrical conductance and the binding energies of the studied molecular wires. In agreement with experimental results, BT-terminated oligoynes are predicted to have a high electrical conductance. The experimental attenuation constants ßH range between 1.7 nm(-1) (CN) and 3.2 nm(-1) (SH) and show the following trend: ßH(CN) < ßH(NH2) < ßH(BT) < ßH(PY) ≈ ßH(SH). DFT-based calculations yield lower values, which range between 0.4 nm(-1) (CN) and 2.2 nm(-1) (PY).

Single molecular conductance of tolanes: experimental and theoretical study on the junction evolution dependent on the anchoring group.

Employing a scanning tunneling microscopy based beak junction technique and mechanically controlled break junction experiments, we investigated tolane (diphenylacetylene)-type single molecular junctions having four different anchoring groups (SH, pyridyl (PY), NH(2), and CN) at a solid/liquid interface. The combination of current-distance and current-voltage measurements and their quantitative statistical analysis revealed the following sequence for junction formation probability and stability: PY > SH > NH(2) > CN. For all single molecular junctions investigated, we observed the evolution through multiple junction configurations, with a particularly well-defined binding geometry for PY. The comparison of density functional theory type model calculations and molecular dynamics simulations with the experimental results revealed structure and mechanistic details of the evolution of the different types of (single) molecular junctions upon stretching quantitatively.

Correlation of breaking forces, conductances and geometries of molecular junctions.

Electrical and mechanical properties of elongated gold-molecule-gold junctions formed by tolane-type molecules with different anchoring groups (pyridyl, thiol, amine, nitrile and dihydrobenzothiophene) were studied in current-sensing force spectroscopy experiments and density functional simulations. Correlations between forces, conductances and junction geometries demonstrate that aromatic tolanes bind between electrodes as single molecules or as weakly-conductive dimers held by mechanically-weak π - π stacking. In contrast with the other anchors that form only S-Au or N-Au bonds, the pyridyl ring also forms a highly-conductive cofacial link to the gold surface. Binding of multiple molecules creates junctions with higher conductances and mechanical strengths than the single-molecule ones.

A quantum circuit rule for interference effects in single-molecule electrical junctions.

A quantum circuit rule for combining quantum interference effects in the conductive properties of oligo(phenyleneethynylene) (OPE)-type molecules possessing three aromatic rings was investigated both experimentally and theoretically. Molecules were of the type X-Y-X, where X represents pyridyl anchors with para (p), meta (m) or ortho (o) connectivities and Y represents a phenyl ring with p and m connectivities. The conductances GXmX (GXpX) of molecules of the form X-m-X (X-p-X), with meta (para) connections in the central ring, were predominantly lower (higher), irrespective of the meta, para or ortho nature of the anchor groups X, demonstrating that conductance is dominated by the nature of quantum interference in the central ring Y. The single-molecule conductances were found to satisfy the quantum circuit rule Gppp/Gpmp=Gmpm/Gmmm. This demonstrates that the contribution to the conductance from the central ring is independent of the para versus meta nature of the anchor groups.

An approach to measure electromechanical properties of atomic and molecular junctions.

We describe a new setup for simultaneous measurements of force and current in conductive nanocontacts in a liquid environment with a high sampling rate and resolution. A lab-built current-to-voltage converter allows measurements of the current over seven orders of magnitude. As examples, we studied conductances and mechanical forces upon formation and breaking of gold atomic contacts and of two molecular junctions containing 1,2-di(4-pyridyl)ethyne (M1) and 1,4-di(4-pyridyl)buta-1,3-diyne (M2). We found that the forces required to deform or break gold atomic contacts depend critically on the surrounding medium. Further, they show non-linear behaviour in dependence of the number N of gold atoms detached. The electromechanical properties of the two types of molecular junctions upon stretching were analysed by correlating breaking forces with simultaneously measured junction conductances. A rather complex behaviour in a wide range of forces was discovered. Comparison of the current-probe atomic force microscopy experiments on the rupture of molecular junctions with STM-based break junction experiments enables the assignment of breaking forces of molecular junctions to the corresponding junction conductances.