Jürgen P. Rabe

Commensurability and Mobility in Two-Dimensional Molecular Patterns on Graphite

Two-dimensional molecular patterns were obtained by the adsorption of long-chain alkanes, alcohols, fatty acids, and a dialkylbenzene from organic solutions onto the basal plane of graphite. In situ scanning tunneling microscopy (STM) studies revealed that these molecules organize in lamellae with the extended alkyl chains oriented parallel to a lattice axis within the basal plane of graphite. The planes of the carbon skeletons, however, can be oriented either predominantly perpendicular to or predominantly parallel with the substrate surface, causing the lamellar lattice to be either in or near registry with the substrate (alkanes and alcohols) or not in registry (fatty acids and dialkylbenzenes). In the case of the alcohols and the dialkylbenzene the molecular axes are tilted by +30� or –30� with respect to an axis normal to the lamella boundaries, giving rise to molecularly well-defined domain boundaries. Fast STM image recording allowed the spontaneous switch between the two tilt angles to be observed in the alcohol monolayers on a time scale of a few milliseconds.

Orientation-dependent ionization energies and interface dipoles in ordered molecular assemblies

Although an isolated individual molecule clearly has only one ionization potential, multiple values are found for molecules in ordered assemblies. Photoelectron spectroscopy of archetypical pi-conjugated organic compounds on metal substrates combined with first-principles calculations and electrostatic modelling reveal the existence of a surface dipole built into molecular layers. Conceptually different from the surface dipole at metal surfaces, its origin lies in details of the molecular electronic structure and its magnitude depends on the orientation of molecules relative to the surface of an ordered assembly. Suitable pre-patterning of substrates to induce specific molecular orientations in subsequently grown films thus permits adjusting the ionization potential of one molecular species over up to 0.6 eV via control over monolayer morphology. In addition to providing in-depth understanding of this phenomenon, our study offers design guidelines for improved organic-organic heterojunctions, hole- or electron-blocking layers and reduced barriers for charge-carrier injection in organic electronic devices.

Synthesis and Self-Assembly of Functionalized Hexa-peri-hexabenzocoronenes

Monolayers of hexa-alkyl substituted derivatives of hexa-peri-hexabenzocoronene (HBC) 1b have previously been investigated by scanning tunneling microscopy (STM) and scanning tunneling spectroscopy (STS). It is expected that different functional groups (electron donating or withdrawing) connected to the aromatic core will influence the packing pattern and possibly the current-voltage characteristics as well. In order to provide suitable model systems, a new synthetic approach to synthesize functionalized HBC derivatives has been developed. This was accomplished by [4 + 2]-cycloaddition of suitably bromo-substituted diphenylacetylenes and 2,3,4,5-tetraarylcyclopenta-2,4-dien-1-ones followed by an oxidative cyclodehydrogenation with iron(III) chloride/nitromethane. Using this strategy three different substitution patterns were synthesized: 2-bromo-5,8,11.14,17-pentadodecylhexa-pecri-hexabenzocoronene (2a), 2,5-dibromo-8,11,14,17-pentadodecylhexa-peri-hexabenzocoronene (2b), and 2,11-dibromo5,8,14,17-pentadodecylhexa-peri-hexa-benzocoronene (2c). These bromo-substituted HBC derivatives were subjected to palladium catalyzed coupling reactions to give donor (alkoxy, amino) as well as acceptor (ester, cyano) substituted derivatives. The self-assembly of these new HBC derivatives was studied in the bulk as well as at an interface. DSC, optical microscopy, and X-ray diffraction revealed the existence of columnar mesophases. The bulk structure in the mesophase is largely insensitive to changes of the substitution pattern; however, in situ scanning tunneling microscopy at the solid-fluid interface between an organic solution of the HBC derivative and highly oriented pyrolytic graphite reveals different packing patterns of the first adsorbed monolayer.

Helical Nanofilament Phases

Packing Bananas and Boomerangs Assembling achiral molecules typically generates achiral domains. However, odd things can happen when the molecules are banana-or boomerang-shaped—their cores can twist out of plain to form left- or right-handed helices, which can then pack into chiral domains that will polarize light (see the Perspective by Amabilino). Hough et al. (p. 452) show that if you make the situation even more complex by frustrating the packing of adjacent layers, you can create a material that appears to be macroscopically isotropic with only very local positional and orientational ordering of the molecules but still shows an overall chirality. In a second paper, Hough et al. (p. 456) also show that if you change the chemistry of the molecules to allow for better overall packing, you can create a situation where helical filaments form that also tend to pack in layered structures. However, the frustration between the two types of packing leads to macroscopically chiral and mesoporous structures. Molecules lacking handedness can form layered, mesoporous helical structures. In the formation of chiral crystals, the tendency for twist in the orientation of neighboring molecules is incompatible with ordering into a lattice: Twist is expelled from planar layers at the expense of local strain. We report the ordered state of a neat material in which a local chiral structure is expressed as twisted layers, a state made possible by spatial limitation of layering to a periodic array of nanoscale filaments. Although made of achiral molecules, the layers in these filaments are twisted and rigorously homochiral—a broken symmetry. The precise structural definition achieved in filament self-assembly enables collective organization into arrays in which an additional broken symmetry—the appearance of macroscopic coherence of the filament twist—produces a liquid crystal phase of helically precessing layers.

Nanographenes as active components of single-molecule electronics and how a scanning tunneling microscope puts them to work.

Single-molecule electronics, that is, realizing novel electronic functionalities from single (or very few) molecules, holds promise for application in various technologies, including signal processing and sensing. Nanographenes, which are extended polycyclic aromatic hydrocarbons (PAHs), are highly attractive subjects for studies of single-molecule electronics because the electronic properties of their flat conjugated systems can be varied dramatically through synthetic modification of their sizes and topologies. Single nanographenes provide high tunneling currents when adsorbed flat onto conducting substrates, such as graphite. Because of their chemical inertness, nanographenes interact only weakly with these substrates, thereby preventing the need for special epitaxial structure matching. Instead, self-assembly at the interface between a conducting solid, such as the basal plane of graphite, and a nanographene solution generally leads to highly ordered monolayers. Scanning tunneling spectroscopy (STS) allows the current-voltage characteristics to be measured through a single molecule positioned between two electrodes; the key to the success of STS is the ability to position the scanning tunneling microscopy (STM) tip freely with respect to the molecule in all dimensions, that is, both parallel and perpendicular to the surface. In this Account, we report the properties of nanographenes having sizes ranging from 0.7 to 3.1 nm and exhibiting various symmetry, periphery, and substitution types. The size of the aromatic system and the nature of its perimeter are two essential features affecting its HOMO-LUMO gap and charge carrier mobility in the condensed phase. Moreover, the extended pi area of larger substituted PAHs improves the degree of self-ordering, another key requirement for high-performance electronic devices. Self-assembly at the interface between an organic solution and the basal plane of graphite allows deposition of single molecules within the well-defined environment of a molecular monolayer. We have used STM and STS to investigate both the structures and electronic properties of these single molecules in situ. Indeed, we have observed key electronic functions, rectification and current control through single molecules, within a prototypical chemical field-effect transistor at ambient temperature. The combination of nanographenes and STM/STS, with the PAHs self-assembled in oriented molecular mono- or bilayers at the interface between an organic solution and the basal plane of graphite and contacted by the STM tip, is a simple, reliable, and versatile system for developing the fundamental concepts of molecular electronics. Our future targets include fast reversible molecular switches and complex molecular electronic devices coupled together from several single-molecule systems.

Molecular dynamics simulations of ordered alkane chains physisorbed on graphite

Scanning tunneling microscopy (STM) studies at the interface between the basal plane of graphite and organic solutions or melts of long chain alkanes and alkyl derivatives reveal that the molecules order in lamellae with the main molecular axes oriented parallel to the substrate. Here we employ molecular dynamics (MD) simulations to obtain more details on the molecular order and dynamics within the alkane lamellae as a function of density. We find that the orientation of the molecular carbon zigzag planes relative to the graphite is governed by a subtle interplay of packing and entropic effects. In addition, we consider multiple layer adsorption and investigate the rapid loss of order with increasing distance from the interface. Finally, we study the diffusive behavior of an isolated long chain alkane, C350H702, on graphite, which is of interest in the context of STM imaging of isolated macromolecules at interfaces. The sensitive dependence on atomic parameters renders MD simulations a valuable complement...

Uniform exciton fluorescence from individual molecular nanotubes immobilized on solid substrates

Self-assembled quasi one-dimensional nanostructures of pi-conjugated molecules may find a use in devices owing to their intriguing optoelectronic properties, which include sharp exciton transitions, strong circular dichroism, high exciton mobilities and photoconductivity. However, many applications require immobilization of these nanostructures on a solid substrate, which is a challenge to achieve without destroying their delicate supramolecular structure. Here, we use a drop-flow technique to immobilize double-walled tubular J-aggregates of amphiphilic cyanine dyes without affecting their morphological or optical properties. High-resolution images of the topography and exciton fluorescence of individual J-aggregates are obtained simultaneously with polarization-resolved near-field scanning optical microscopy. These images show remarkably uniform supramolecular structure, both along individual nanotubes and between nanotubes in an ensemble, demonstrating their potential for light harvesting and energy transport.

The orientation of Langmuir–Blodgett monolayers using NEXAFS

Carbon K‐shell NEXAFS (near edge x‐ray absorption fine structure) spectra of oriented hydrocarbon chains in Langmuir–Blodgett (LB) monolayers were measured and used to study the orientation of these molecules. The LB monolayers were assembled from arachidic acid or cadmium or calcium arachidate on the oxidized Si(111) surface. The observed NEXAFS resonances are assigned to transitions to excited states which are localized on individual CH2 groups or C–C bonds. From a detailed analysis using curve‐fitting techniques of the angular dependence of the various spectral peaks, the hydrocarbon chains of the cadmium arachidate monolayer is estimated to lie within 15° of the surface normal, the hydrocarbon chains of the calcium arachidate monolayer is estimated to be tilted by 33±5° from the surface normal, while the arachidic acid monolayer is not ordered at all. The determined chain orientations are discussed in terms of a microscopic model involving lateral interactions between the zig–zag hydrocarbon chains.

Self-Assembly of a Conjugated Polymer: From Molecular Rods to a Nanoribbon Architecture with Molecular Dimensions

Candidates for molecular nanowires for the interconnection of gold nanoelectrodes in a molecular-scale electronic device are to be found in end-functionalised poly(para-phenyleneethynylene)s. The self-assembly of these polymers was studied on atomically flat solid substrates. On graphite, sub-molecularly resolved imaging with scanning tunneling microscopy revealed nanorods in a 2 D nematic-like texture, while on mica, scanning force microscopy (see picture) shows that the nanorods can self-assemble into highly oriented micrometer-long nanoribbons with a molecular cross-section.

The Self‐Assembly of Lipophilic Guanosine Derivatives in Solution and on Solid Surfaces

The self-assembly of lipophilic deoxyguanosine derivatives 1 and 2 has been studied in solution by NMR spectroscopy and ESI-MS (electrospray ionization mass spectrometry). NMR data show the existence of two types of self-assembled, ribbonlike structures (A and B), which are connected at the guanine moieties through two different H-bonded networks. The first species (A), which is stable in the solid state and characterised by cyclic NH(2)-O(6) and NH(1)-N(7) hydrogen bonds, is detected soon after dissolving the polycrystalline powder in rigorously anhydrous CDCl3. In solution it slowly undergoes a structural transition towards a thermodynamically stable ribbon characterised by NH(1)-O(6) and NH(2)-N(3) cyclic hydrogen bonds (B). On the other hand, at surfaces, self-assembled ribbon nanostructures have been grown from solutions of derivative 1 both on mica and at the graphite-solution interface. They have been investigated by means of tapping mode scanning force microscopy (SFM) and scanning tunnelling microscopy (STM), respectively. SFM revealed dry, micrometer-long nanoribbons with a molecular cross-section. while STM imaging at submolecular resolution indicates a molecular packing of type A, like the one detected in the solid state. This indicates that, upon adsorption at the solid-liquid interface, the guanosine moieties undergo a structural rearrangement from a B-type to an A-type ribbon.