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Tetrabromo aromatics can be synthesized by the Fischer-Zimmermann condensation of appropriate pyrylium salts with arylene dicarboxylic acid salts. Their cyclization by intramolecular Yamamoto coupling yields strained bicyclophanes with adjustable sizes and different intraannular bridges. All compounds adsorb at the solid/liquid interface on highly oriented pyrolytic graphite (HOPG) and are investigated by scanning tunneling microscopy (STM) with submolecular resolution. The observed two-dimensional (2D) supramolecular nanopatterns depend only on the sizes and alkoxy periphery of the cyclophanes and are independent of the specific structures of the intraannular bridges. Since the central arylene moieties of the smaller species are oriented perpendicular to the planes of the bicyclophanes, their substituents protrude from the surface by up to 1.6 nm after adsorption. Therefore, these molecules are attractive platforms for addressing the volume phase above the graphite surface.

All-phenylene molecular spoked wheels, cutouts of graphenylene-3, have been synthesized by intramolecular Yamamoto coupling of the respective dodecabromides. The uneven number of aromatics at the sides of the wheels requires a non-D6h symmetric precursor that is available via Vollhardt trimerization of an unsymmetrically substituted acetylene. The coupling gives a considerably lower yield. This is attributable to a supramolecular aggregation of the ring precursors during the coupling process that gives rise to an intermolecular dimer and oligomer formation. Larger side groups allow us to diminish this problem to a certain extent and increase the wheel yield. Scanning tunneling microscopy investigations clearly reveal the structures of the compounds with submolecular resolution and reflect the aggregation behavior. Time-resolved photoluminescence spectroscopy shows that there is no energy transfer from the rim to the spokes of the wheels due to an interruption of the conjugation at the center of the molecules.

Molecular spoked wheels with intraannular functionalizable pillars are synthesized in a modular approach. The functionalities at their ends are variable, and a propargyl alcohol, a [6,6]-phenyl-C61-butyrate, and a perylene monoimide are investigated. All compounds form two-dimensional crystals on highly oriented pyrolytic graphite at the solid-liquid interface. As determined by submolecularly resolved scanning tunneling microscopy, the pillars adopt equilibrium distances of 6.0 nm. The fullerene has a residual mobility, limited by the length of the flexible connector unit. The experimental results are supported and rationalized by molecular dynamics simulations. These also show that, in contrast, the more rigidly attached perylene monoimide units remain oriented along the surface normal and maintain a smallest distance of 2 nm above the graphite substrate. The robust packing concept also holds for cocrystals with molecular hexagons that expand the pillar-pillar distances by 15 % and block unspecific intercalation.

Supramolecular nanopatterns of arylene–alkynylene squares with side chains of different lengths are investigated by scanning tunneling microscopy at the solid/liquid interface of highly oriented pyrolytic graphite and 1,2,4-trichlorobenzene. Self-sorting leads to the intermolecular interdigitation of alkoxy side chains of identical length. Voids inside and between the squares are occupied by intercalated solvent molecules, which numbers depend on the sizes and shapes of the nanopores. In addition, planar and non-planar coronoid polycyclic aromatic hydrocarbons (i.e., butyloxy-substituted kekulene and octulene derivatives) are found to be able to intercalate into the intramolecular nanopores.

Molecular spoked wheels with D3h and Cs symmetry are synthesized by Vollhardt trimerization of C2v-symmetric dumbbell structures with central acetylene units and subsequent intramolecular ring closure. Scanning tunneling microscopy of the D3h-symmetric species at the solid/liquid interface on graphite reveals triporous chiral honeycomb nanopatterns in which the alkoxy side chains dominate the packing over the carboxylic acid groups, which remain unpaired. In contrast, Cs-symmetric isomers partially allow for pairing of the carboxylic acids, which therefore act as a probe for the reduced alkoxy chain nanopattern stabilization. This observation also reflects the adsorbate substrate symmetry mismatch, which leads to an increase of nanopattern complexity and unexpected templating of alkoxy side chains along the graphite armchair directions. State-of-the-art GFN-FF calculations confirm the overall structure of this packing and attribute the unusual side-chain orientation to a steric constraint in a confined environment. These calculations go far beyond conventional simple space-filling models and are therefore particularly suitable for this special case of molecular packing., Scanning tunneling microscopy investigations of phenylene-based molecular spoked wheels with D3h and Cs symmetries on graphite show the competitive or complementary effects of carboxylic acid groups and alkoxy chains on the nanopattern formation.

Donor–acceptor-type interactions between π-electron systems are of high relevance in the design of chemical sensors. Due to their electron-rich nature, cyclic trinuclear complexes (CTCs) of gold(I) are ideal receptor sites for electron-deficient aromatic analytes. Scanning tunneling microscopy provided insight into the structures of two-dimensional crystals of pyridinate gold CTCs that form on a graphite template at the solid/liquid interface. One polymorph thereof – in turn – templated the on-top co-adsorption of π-acidic pyrazolate CTCs as electron-poor guests up to a certain threshold. From NMR titration experiments, we quantified free energies of −6.1 to −7.5 kcal mol−1 for the binding between pyridinate gold(I) CTCs and π-acidic pyrazolate CTCs. Quantum chemical calculations revealed that these interactions are largely dominated by London dispersion. These results give a more detailed insight into a rational design of sensitive CNT- or graphene-based sensors for π-acidic analytes, such as electron-deficient aromatics.

Molecular spoked wheels with an all-phenylene backbone and different alkoxy side chain substitution patterns were synthesized using a cobalt-catalyzed [2 + 2 + 2] cycloaddition and subsequent template-directed cyclization via Yamamoto coupling. The two-dimensional organization of the molecules at the solid/liquid interface was investigated by means of scanning tunneling microscopy, allowing imaging of the molecular structure with submolecular resolution. With the right proportion of the flexible alkyl corona to the rigid core, mesomorphic behavior of one compound could be observed over a wide temperature range.

Strong dipole–dipole coupling within and between π‐conjugated segments shifts electronic transitions, and modifies vibronic coupling and excited‐state lifetimes. Since J‐type coupling between monomers along the conjugated‐polymer (CP) chain and H‐type coupling of chromophores between chains of a CP compete, a superposition of the spectral modifications arising from each type of coupling emerges, making the two couplings hard to discern in the ensemble. We introduce a single‐molecule H‐type aggregate of fixed spacing and variable length of up to 10 nm. HJ‐type aggregate formation is visualized intuitively in the scatter of single‐molecule spectra., Coupling therapy: In organic electronics, J‐type coupling between monomers along the chain and H‐type coupling of chromophores between chains compete, which makes the two types of coupling hard to discern in the ensemble. A single‐molecule H‐type aggregate of fixed spacing and variable length of up to 10 nm is introduced, and HJ‐type aggregate formation is visualized intuitively in the scatter of single‐molecule spectra.

Alkyl- and alkoxy-substituted p-phenylene–butadiynylene tetramers, obtained via a stepwise synthesis, are polymerized under Glaser coupling conditions. The fractionation of the oligomers by recycling gel permeation chromatography (recGPC) yields three sets of monodisperse oligo(p-phenylene–butadiynylene)s (OPBs) with degrees of polymerization n = 4, 8, 12, ..., 60. Subsequent GPC analysis of these oligomers provides three sets of size- and substituent-dependent conversion factors that quantify the overestimation of the oligomer molecular weight when a polystyrene (PS) calibrated GPC system is used for the data analysis. Scanning tunneling microscopy (STM) of representative oligomers at the solid/liquid interface visualizes the monodispersity, the length-dependent rigidity, and their assembling behavior.

Macrocycles with quaterthiophene subunits were obtained by cyclooligomerization by direct oxidative coupling of unsubstituted dithiophene moieties. The rings were closed with high selectivity by an α,β′-connection of the thiophenes as proven by NMR spectroscopy. The reaction of the precursor with terthiophene moieties yielded the symmetric α,α′-linked macrocycle in low yield together with various differently connected isomers. Blocking of the β-position of the half-rings yielded selectively the α,α′-linked macrocycle. Selected cyclothiophenes were investigated by scanning tunneling microscopy, which displayed the formation of highly ordered 2D crystalline monolayers.

Alkoxy-substituted phenylene–ethynylene–butadiynylenes (PEBs) are connected via 1H-benzimidazole units to form H-shaped molecular scaffolds that self-assemble on graphite at the solid/liquid interface. Spacer lengths and end groups determine supramolecular tiling patterns, as shown via scanning tunneling microscopy (STM).

We employ five π-conjugated model materials of different molecular shape-oligomers and cyclic structures-to investigate the extent of exciton self-trapping and torsional motion of the molecular framework following optical excitation. Our studies combine steady state and transient fluorescence spectroscopy in the ensemble with measurements of polarization anisotropy on single molecules, supported by Monte Carlo simulations. The dimer exhibits a significant spectral red shift within ∼100 ps after photoexcitation which is attributed to torsional relaxation. This relaxation mechanism is inhibited in the structurally rigid macrocyclic analogue. However, both systems show a high degree of exciton localization but with very different consequences: while, in the macrocycle, the exciton localizes randomly on different parts of the ring, scrambling polarization memory, in the dimer, localization leads to a deterministic exciton position with luminescence characteristics of a dipole. Monte Carlo simulations allow us to quantify the structural difference between the emitting and absorbing units of the π-conjugated system in terms of disorder parameters.

Inter- or intramolecular coupling processes between chromophores such as excimer formation or H- and J-aggregation are crucial to describing the photophysics of closely packed films of conjugated polymers. Such coupling is highly distance dependent and should be sensitive to both fluctuations in the spacing between chromophores as well as the actual position on the chromophore where the exciton localizes. Single-molecule spectroscopy reveals these intrinsic fluctuations in well-defined bichromophoric model systems of cofacial oligomers. Signatures of interchromophoric interactions in the excited state--spectral red shifting and broadening and a slowing of photoluminescence decay--correlate with each other but scatter strongly between single molecules, implying an extraordinary distribution in coupling strengths. Furthermore, these excimer-like spectral fingerprints vary with time, revealing intrinsic dynamics in the coupling strength within one single dimer molecule, which constitutes the starting point for describing a molecular solid. Such spectral sensitivity to sub-Ångström molecular dynamics could prove complementary to conventional FRET-based molecular rulers.

The modular synthesis of a defined, rigid molecular spoked wheel structure with the sum formula C1878H2682 and a diameter of about 12 nm is described. The attached 96 dodecyl side chains provide the solubility of the 25 260 Da compound in common organic solvents. At the octanoic acid/highly oriented pyrolytic graphite interface, the molecules self-assemble to form an ordered 2D lattice, which is investigated by scanning tunneling microscopy, displaying their structure with submolecular resolution.

Self-assembled monolayers of a molecular spoked wheel (a shape-persistent macrocycle with an intraannular spoke/hub system) and its synthetic precursor are investigated by scanning tunneling microscopy (STM) at the liquid/solid interface of 1-octanoic acid and highly oriented pyrolytic graphite. The submolecularly resolved STM images reveal that the molecules indeed behave as more or less rigid objects of certain sizes and shapes – depending on their chemical structures. In addition, the images provide insight into the multilayer growth of the molecular spoked wheels (MSWs), where the first adlayer acts as a template for the commensurate adsorption of molecules in the second layer.

We present the efficient synthesis of a new molecular spoked-wheel structure (MSW-3). Two derivatives with diameters of approximately 4 nm have been prepared. By highlighting the importance of pseudo-high-dilution conditions during cyclization, we were able to access the compounds on a several hundred milligram scale. In addition to the standard characterization (NMR spectroscopy, MS), we describe a detailed investigation of the optical properties of the fluorescent MSWs by comparison with appropriate model chromophores. Furthermore, a comprehensive study of the structure in solution by means of light- and X-ray scattering experiments has been conducted. Scanning tunneling microscopy (STM) revealed the two-dimensional organization of the molecules on highly oriented pyrolytic graphite and emphasized the spoked-wheel structure. The diameter of these molecules measured by small-angle X-ray scattering is in very good agreement with that obtained from STM and matches the results of molecular modeling. This confirms the rigidifying effect of the spokes, which results in highly shape-persistent nanometer-sized oblate organic compounds.

We report the stepwise assembly of supramolecular daisy chain rotaxanes (DCR) made of double‐stranded DNA: Small dsDNA macrocycles bearing an axle assemble into a pseudo‐DCR precursor that was connected to rigid DNA stoppers to form DCR with the macrocycles hybridized to the axles. In presence of release oligodeoxynucleotides (rODNs), the macrocycles are released from their respective hybridization sites on the axles, leading to stable mechanically interlocked DCRs. Besides the expected threaded DCRs, certain amounts of externally hybridized structures were observed, which dissociate into dumbbell structures in presence of rODNs. We show that the genuine DCRs have significantly higher degrees of freedom in their movement along the thread axle than the hybridized DCR precursors. Interlocking of DNA in DCRs might serve as a versatile principle for constructing functional DNA nanostructures where the movement of the subunits is restricted within precisely confined tolerance ranges.

Molecular polygons with three to six sides and binary mixtures thereof form long-range ordered patterns at the TCB/HOPG interface. This includes also the 2D crystallization of pentagons. The results provide an insight into how the symmetry of molecules is translated into periodic structures.

Shape-persistent rigid phenylene-ethynylene-butadiynylenes form lamellar self-assembled monolayers (SAMs) at the HOPG/TCB interface, which were studied by scanning tunneling microscopy (STM) with submolecular resolution. Substitution of the terminating acetylene functions with polar cyanopropyldimethylsilyl groups leads to 2D phase separation and defined rod-rod interactions, which determine the packing distances between the rigid rods. The results stimulated the connection of rigid rods via septiarylene clamp units. They covalently link two rigid rod units and define the intramolecular rod-rod distance that matches the alkoxy substituent chain lengths. The systems can be described as half-ring structures of two rigid rods connected via a rotatable joint unit. These acetylene-terminated half-ring structures were also oligomerized under Cu and Pd catalysis to yield defined acyclic and cyclic oligomers. Detailed STM studies decoded the molecular origin of the surface patterning of such systems. The dodecyloxy side chains are adsorbed along the HOPG main axes and, together with the alkoxy backbone angle, determine the adsorption direction of the adlayers.

A series of dithienophenazines with different lengths of the oligomeric thiophene units (quaterthiophenes and sexithiophenes) was synthesized. The thiophene and phenazine units act as electron donors and acceptors, respectively, resulting in characteristic absorption spectra. The optical spectra were calculated using time-dependent density functional theory at the B3LYP/TZVP level and verify the experimental data. Adsorption of the dithienophenazines on highly ordered pyrolytic graphite (HOPG) was investigated by scanning tunneling microscopy, showing that one of the compounds forms highly organized self-assembled monolayers.

We report about new easy-to-synthesize deep blue light-emitting organic materials. Various substituted low-molecular-weight triphenylene-derivatives have been prepared in a one-step procedure and are easily available on large scale and high purity. Furthermore, the synthesis of an oxetane functionalized, photo-crosslinkable triphenylene-based emitter material with enhanced film-forming properties is described. The low-molecular-weight emitters were vacuum-deposited, whereas the photo-crosslinkable emitter material derivative was processed from solution. The optical and electrical properties of the compounds were investigated. The corresponding photoluminescence emission spectra exhibit λmax,ems values around 400 nm. Organic light-emitting multi layer devices were fabricated and characterized. OLED devices from these molecules emit deep blue light of 436–456 nm.

Ga+ focused ion beam (FIB) patterning was used to structure highly oriented pyrolytic graphite surfaces with square, periodic arrays of amorphous carbon defects (mesh sizes: 300 nm–2 µm). Controlled oxygen etching of these arrays leads to matrices of uniform, orientationally aligned, nm-sized, hexagonal holes. The properties of the resulting hole assembly (hole depths and lateral hole dimensions) have been investigated by means of atomic force microscopy, scanning electron microscopy and FIB sectioning. The hole dimensions and uniformity both depend on the FIB parameters and etching conditions. Etching temperatures from 500 to 700 °C were applied. Initial etch rates of up to 106 C s−1 per individual hole were observed when using oxygen pressures of 200 mbar. For an etch temperature of 590 °C the rate of etching of individual holes was found to depend measurably on the inter-hole separation. This confirms that the associated reaction kinetics is mediated by the finite diffusion length of reactive oxygen species along the graphite basal plane. Prolonged etching results in hole–hole contact and generation of mesa arrays of controllable size and shape.

Seeing stars: The two-dimensional patterns of the polycyclic heteroaromatic star molecules 1 on graphite vary with the side chain length. For n=12, frustrated self-assembly leads to hierarchically organized superstructures: up to 10 molecules form triangular aggregates which pack densely into hexagonal patterns with very large (15.5 nm) lattice constants.

The interactions between two π-conjugated oligomers templated in molecular scaffolds are revealed as a function of separation and orientation, providing models of intermolecular interactions in bulk organic semiconductor materials. For a variety of dimer geometries (acyclic and macrocyclic) of the same model oligomer, no change in fluorescence spectra, fluorescence dynamics, or low-temperature single-molecule emission characteristics is observed. A small red-shift and slowing of fluorescence in the most closely spaced macrocyclic dimer structure is thought to arise both due to an intramolecular solvatochromic shift as well as from weak intramolecular aggregate formation. No corresponding effect is observed in bulk films of the acyclic model oligomer, implying the absence of intermolecular aggregate or excimer formation due to random relative dipole orientations. The largest effect of intramolecular geometry of the model dimer structures is seen in transient fluorescence depolarization, where an open ring geometry leads to rapid depolarization, compared to the corresponding macrocycle, due to the presence of a range of molecular transition dipole moment orientations. Self-assembled monolayers of the molecules on HOPG investigated by scanning-tunneling microscopy further illustrate the conformational variability of the open dimers in contrast to the fixed conformation of the closed dimers.

A route towards phenylene-thiophene macrocycles (IV) via oxidative thiophene coupling under pseudo-high dilution conditions is reported.

Rigid rod oligo(phenylene-ethynylene-butadiynylene)s (oPEBs), “half-rings” of two rigid rods connected via a molecular clamp unit, and shape-persistent macrocycles (cyclic “half-ring dimers”) are synthesized and their self-assembled monolayers (SAMs) are investigated by scanning tunneling microscopy (STM) at the interface of 1,2,4-trichlorobenzene (TCB)/highly oriented pyrolytic graphite (HOPG). The results are important for the design of molecular building blocks for two-dimensional nanoscale architectures on solid surfaces.

The emission mechanisms in extragalactic jets include synchrotron and various inverse-Compton processes. At low (radio through infrared) energies, it is widely agreed that synchrotron emission dominates in both low-power (FR I) and high-power (FR II and quasar) jets, because of the power-law nature of the spectra observed and high polarizations. However, at higher energies, the emission mechanism for high-power jets at kpc scales is hotly debated. Two mechanisms have been proposed: either inverse-Compton of cosmic microwave background photons or synchrotron emission from a second, high-energy population of electrons. Here we discuss optical polarimetry as a method for diagnosing the mechanism for the high-energy emission in quasar jets, as well as revealing the jet's three-dimensional energetic and magnetic field structure. We then discuss high-energy emission mechanisms for powerful jets in the light of the HST polarimetry of PKS 1136-135., 4 pages, 1 figure. To appear in proceedings of "The Monster's Fiery Breath: Feedback in galaxies, groups, and clusters" meeting, June 1-5, 2009 held in Madison, WI, USA

The reaction of solid C(58) films with atomic deuterium to yield deuterofullerenes, C(58)D(x), has been investigated by thermal desorption spectroscopy coupled with mass spectrometric detection, ultraviolet photoionization spectroscopy (21.2 eV), and atomic force microscopy (AFM). The average composition of the deuterofullerenes created depends on deuterium dose, beam flux, and surface temperature. Low deuterium exposures at room temperature yield predominantly C(58)D(6-8) cages. Saturation exposures at room temperature yield mass spectra peaked at C(58)D(26). After saturation exposures at elevated surface temperatures (approximately 500 K), the (subsequently) desorbed material reveals a comparatively narrow mass spectral distribution centered at C(58)D(30). Deuteration is associated with cleavage of covalent cage-cage bonds in the starting C(58) oligomer material, as evidenced by a considerable lowering of the sublimation energies of C(58)D(x) compared to desorption of C(58) desorbed from pure oligomer films. Correspondingly, AFM images reveal a D-induced, thermally activated transition from dendritic C(58) oligomer islands into smooth-rimmed islands composed of deuterated cages. Deuterated films exhibit a significantly lower work function than bare C(58) films. Progressing deuteration also gradually raises the surface ionization potential.

Novel semiconducting materials have been prepared under ultrahigh-vacuum conditions by soft-landing mass-selected Cn+ (50or =n60; even n) on highly oriented pyrolytic graphite surfaces at mean kinetic energies of 6 eV. In all cases, Cn films grow according to the Volmer-Weber mechanism: the surface is initially decorated by two-dimensional fractal islands, which in later deposition stages become three-dimensional dendritic mounds. We infer that Cn aggregation is governed by reactive sites comprising adjacent pentagons (or heptagons) on individual cages. The resulting covalent cage-cage bonds are responsible for the unusually high thermal stability of the films compared to solid C60. The apparent activation energies for intact Cn sublimation range from 2.2 eV for C58 to 2.6 eV for C50 as derived from thermal desorption spectra. All Cn films exhibit a common valence-band ultraviolet photoelectron spectroscopy spectral feature located around the center of a broad highest occupied molecular-orbital (HOMO)-derived band (EB approximately 2.5 eV). This feature has been assigned to Cn units covalently linked to each other in polymeric structures. To within experimental accuracy, the same work function (4.8 eV) was determined for thick films of all Cn studied. In contrast, "HOMO" ionization potentials were cage size dependent and significantly lower than that obtained for C60. C58 exhibited the lowest HOMO (6.5 eV). Band gaps of Cn films have been determined by depositing small amounts of Cs atoms onto the topmost film layer. HOMO-lowest unoccupied molecular-orbital-derived band gaps between 0.8 eV (C52) and 1.8 eV (C50) were observed, compared to 1.5 eV for solid C60.

A new solid material has been created in ultra high vacuum by utilizing the aggregation process of C58 molecules deposited onto highly oriented pyrolytic graphite from a mass selected low-energy ion beam comprising C58+. Cluster fluxes of up to 3 × 1011 ions s−1 cm−2 with impinging kinetic energies of 6 ± 0.5 eV were typically applied. Growth of the solid C58 phase proceeds according to the cluster-aggregation-based Volmer–Weber scenario where initially ramified 2D islands transform into 3D pyramid-like structures at higher coverages. The C58 films created exhibit much higher thermal stability than the C60 solid phase. Sublimation of C58 sets in at a temperature of 700 K. Ultraviolet photoionization spectra (He I, 21.2 eV) yield a molecular ionization potential in the range between 6.6 and 7 eV. Density functional and Hartree–Fock theories suggest that the formation of C58 dimers and higher multimers upon deposition/aggregation gives rise to the high thermal stability and unique electronic properties of this material.

The aggregation of shape-persistent macrocycles with an empty cavity, an undecyldiether strand and a tetraethylene glycol strand leads in all cases to a macroscopic gelation of the solvent. However, the gelation temperatures are fine-tuned by the intraannular substituents.

A route towards phenylene-bithiophene macrocycles via oxidative thiophene coupling under pseudo-high dilution conditions is reported. This method is applied to the synthesis of a shape-persistent thiophene macrocycle with extraannularly attached perylenebisimide moieties that forms supramolecular aggregates at the solid/liquid interface.