We show that molecular wires up to 14 nm in length composed by zinc-porphyrins bridged by bipyridines stand efficient electrical transport. Self-assembled molecular wires were prepared step-by-step, alternating up to 13 units of zinc-octaethylporphyrin with axially coordinated 4,4′-bipyridine, on highly oriented pyrolytic graphite (HOPG). A combination of molecular resolution imaging and scanning tunneling spectroscopy allowed us to follow molecules self-assembly in real time during wire fabrication and to measure wires current, respectively. A statistical analysis of hundreds of current–voltage curves was carried out to determine the conductance of individual porphyrin/bipyridine wires. From the conductance dependence on the wires length an ultra low attenuation factor (β = 0.015 ± 0.006 Å–1) was obtained for shorter wires, with a transition in conduction regime occurring at ca. 6.5 nm long wires.

Nanocorrals created by scanning probe lithography on covalently modified graphite surfaces are used to induce a chiral bias in the enantiomorphic assembly of a prochiral molecule at the liquid/graphite interface. By controlling the orientation of the nanocorrals with respect to the underlying graphite surface, the nanocorral handedness can be freely chosen and thus a chiral bias in molecular self-assembly is created at an achiral surface solely by the scanning probe lithography process.

No abstract

Chemical and structural defects in otherwise pristine materials can result in either improved or degraded material performance. Unfortunately, little is known about the role of these defects on complex hierarchical processes such as self-assembly. Here, the influence of defective surfaces on physisorbed self-assembly occurring at liquid/solid interfaces is investigated. Covalently bound defects on graphite surfaces are generated by electrochemically activating diazonium cations. After creating the defective substrates, a solution containing self-assembling molecules was deposited on the surface. Subsequent scanning probe investigations expose how the chemisorbed molecular units can either be incorporated within a porous hexagonal network, or generate local perturbations in the form of partial or full desorption of the physisorbed molecules. Overall, the chemisorbed molecules alter the local energy landscape for self-assembly to isolate new molecular packing arrangements. With a single-molecule perspective, this work outlines how chemical defects contribute to the formation of metastable assemblies and their evolutionary pathways toward higher-symmetry networks.

A network of self-assembled polystyrene beads was employed as a lithographic mask during covalent functionalization reactions on graphitic surfaces to create nanocorrals for confined molecular self-assembly studies. The beads were initially assembled into hexagonal arrays at the air-liquid interface and then transferred to the substrate surface. Subsequent electrochemical grafting reactions involving aryl diazonium molecules created covalently bound molecular units that were localized in the void space between the nanospheres. Removal of the bead template exposed hexagonally arranged circular nanocorrals separated by regions of chemisorbed molecules. Small molecule self-assembly was then investigated inside the resultant nanocorrals using scanning tunneling microscopy to highlight localized confinement effects. Overall, this work illustrates the utility of self-assembly principles to transcend length scale gaps in the development of hierarchically patterned molecular materials.

Abstract. Organic thin film transistors, using self-standing 50 !m thick chitosan films as dielectric, are fabricated using sublimed pentacene or two conjugated polymers deposited by spin coating as semiconductors. Field-effect mobilities are found to be similar to values obtained with other dielectrics and, in the case of pentacene, a value (0.13 cm 2 /(V·s) comparable to high performing transistors was determined. In spite of the low On/Off ratios (a maximum value of 600 was obtained for the pentacene-based transistors), these are promising results for the area of sustainable organic electronics in general and for biocompatible electronics in particular.

Phase behavior of self-assembled molecular networks is affected by spatial confinement in corrals.

We report on the detection and stabilization of a previously unknown 2D pseudopolymorph of an alkoxy isophthalic acid using lateral nanoconfinement. The self-assembled molecular networks formed by the isophthalic acid derivative were studied at the interface between covalently modified graphite and an organic solvent. When self-assembled on graphite with moderate surface coverage of covalently bound aryl groups, a previously unknown metastable pseudopolymorph was detected. This pseudopolymorph, which was presumably 'trapped' in between the surface bound aryl groups, underwent a timedependent phase transition to the stable polymorph typically observed on pristine graphite. The stabilization of the pseudopolymorph was then achieved by using an alternative nanoconfinement strategy where the domains of the pseudopolymorph could be formed and stabilized by restricting the self-assembly in nanometer-sized shallow compartments produced by STM-based nanolithography carried out on graphite surface carrying a high density of covalently bound aryl groups. These experimental results are supported by molecular mechanics and molecular dynamics simulations which not only provide important insight into the relative stabilities of the different structures but also shed light onto the mechanism of the formation and stabilization of the pseudopolymorph under nanoscopic lateral confinement.