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With the aim of achieving surface-mediated enantioselective adsorption, the self-assembly of chiral oligo(p-phenylenevinylene) (OPV3T) with nucleosides is investigated at the liquid/solid interface by means of scanning tunneling microscopy and molecular modeling. OPV3T enantiomers form mirror related hexameric rosette patterns. The DNA nucleoside, thymidine, does not self-assemble into stable adlayers but coadsorbs with OPV3T on the surface, leading to a pattern transformation of OPV3T from rosettes to dimers, and a change in chiral expression as well. Diastereoselective recognition between OPV3T and thymidine enantiomers can be used to resolve thymidine enantiomers at an achiral surface with an OPV3T enantiomer as the resolving agent. The impact of molar ratio and concentration on the self-assembly and chiral resolution is systematically investigated. Because there is no interaction between OPV3T and thymidine in solution, the liquid/solid interface acts as the platform for the chiral resolution of thymidine enantiomers.

An oligo(p-phenylenevinylene) (OPV)-substituted hexaarylbenzene has been synthesized and fully characterized. Recycling gel permeation chromatography appeared to be a powerful technique to obtain the OPV molecules in a very pure form. X-ray analysis and polarization optical microscopy revealed that the OPV molecule is plastic crystalline at room temperature with an ordered columnar superstructure. In apolar solvents, the molecules self-assemble via a highly cooperative fashion into right-handed chiral superstructures, which are stable even at high temperatures and low concentration. Atomic force microscopy revealed right-handed fibers with a diameter of 6 nm, indicating pi-stacked aggregates; on a silicon oxide substrate, supercoiled chiral structures were observed. STM studies on a liquid-solid interface showed that the star-shaped OPV molecule forms an organized monolayer having a chiral hexagonal lattice.

The arrangement of discotic hexa-peri-hexabenzocoronenes (HBCs) into columnar helical superstructures has been investigated in relation to their molecular architecture. The supramolecular structure of two hexaphenyl-substituted HBC derivatives, differing only in the chiral/achiral nature of the attached alkyl side chains, was studied by circular dichroism and temperature-dependent wide-angle X-ray diffraction on oriented filaments. A structural model in agreement with the experimental observations was developed on the basis of accompanying quantum-chemical calculations. The helical organization along the self-assembled columnar structures was induced by the steric requirements of the bulky phenyl rings near the aromatic core, i.e., by their rotation out-of-plane with respect to the aromatic core. On the other hand, a uniform handedness of the twist was generated by chiral alkyl substituents. At higher temperatures the degree of helical organization decreases due to lateral and longitudinal dynamics of the discotic molecules. Annealing at ambient conditions improved the long-range arrangement of the discs along the columnar structures. This reorganization indicated a self-healing of the plastic material which is desirable for application of discotics as active layers in electronic devices. The helical packing resulted in a considerable stability of the mesophase up to 500 degrees C, which has not been reported for a discotic so far.

Photogeneration quantum yield in layers of discotic liquid crystals (DLC, hole transport material), perylene derivative (electron transport material) and of their mixtures were determined by using surface potential decay technique. While in pure DLC only very weak photogeneration in the visible range was detected, and in pure perylene derivative only negative mobile charge carriers were photogenerated, in the mixtures a synergetic effect of photogeneration of both positive and negative mobile charge carriers was observed. This is because the excitons photogenerated at perylene derivative dissociate into electron–hole pairs, and then electrons are transported via perylene derivative while the holes are transferred onto the DLC molecules. The obtained results were correlated with performance of the photovoltaic devices with active layer made of the mixtures of the DLC and perylene derivative and of their blends with photoconducting polymer. It was found, that the power conversion efficiency of the device is dependent on the film morphology.

The effects of the core size, the side chain length, and the number of substituents on the supramolecular organization of polycyclic aromatic hydrocarbons have been investigated by 2D wide-angle X-ray scattering experiments performed on oriented filaments prepared by extrusion. The aromatic core size of the compounds varied between the hexa-peri-hexabenzocoronene core consisting of 42 carbon atoms and the enlarged aromatic core of 132 carbon atoms, whereas the length of the side chains extended up to 20 carbon atoms per chain. It has been observed that the lateral packing characterized by the lattice constant of the 2D intercolumnar hexagonal arrangement increases with the molecular masses of the core, forming the columnar stacks, and of the side chains which fill the core periphery. A model describing the relationship between the morphological and molecular parameters for the columnar hexagonal arrangements of the discotics is suggested and indeed proven by comparison with the experimental results.

The thermal properties and self-organization of hexa-peri-hexabenzocoronene (HBC) derivatives with dove-tailed alkyl chains of various lengths have been investigated using polarized optical microscopy and wide-angle X-ray scattering. It is shown that the size-related increase of steric interactions among the peripheral side chains substituted to the aromatic core leads to a dramatically lowered isotropization temperature, allowing thermal processing at practical temperatures. Additionally, the introduction of ether linkages within the side chains enhances the affinity of the discotic molecules towards polar surfaces, resulting in homeotropic self-assembly when the compounds are processed from the isotropic state between two surfaces and, for the first time, as a thin film on a single surface. It is established that the degree of homeotropic order is influenced by the phase behavior, the supramolecular order in the bulk, and the surface affinity of the corresponding derivatives. These results are important for the design of photovoltaic cells based on HBC derivatives.

The self-organization of two polycyclic aromatic hydrocarbons with different aromatic core sizes, dodecylphenyl-substituted hexa-peri- hexabenzocoronene and an extended disk consisting of 96 carbon atoms 6-fold-alkyl-substituted, on the surface from solution has been investigated. Highly ordered surface layers of both materials could be obtained by the zone-casting technique, despite an apparently low self-organization in drop-cast films. The zone-cast films revealed high macroscopic uniaxial orientation of the columns with a molecular edge-on arrangement on the glass support as confirmed by polarized optical microscopy, UV-vis measurements in polarized light, high-resolution transmission electron microscopy, and X-ray diffraction. Electron diffraction indicated a high intracolumnar periodicity of the molecules, but a low intercolumnar correlation of the disks due to the increased molecular dynamics in the liquid crystalline phase.

We report on the self-assembly from solutions of a large synthetic polycyclic aromatic hydrocarbon (PAH) on a mica surface partially coated by macroscopic gold electrodes. Isotropic structures, continuous monolayers and interconnected networks have been obtained by varying the deposition conditions, including the type of solvent as well as the temperature of the solution and of the substrate. The growth of these organic–inorganic interfaces is governed by the interplay between intermolecular and interfacial interactions. In this frame, the rate of the solvent evaporation plays an important role as the structural arrangement of the PAH ad-layer on the sub-micrometer scale is controlled by the dewetting process. The presence of the gold electrodes influences the film morphology on mica at distances of tens of micrometers from the electrode border, due to the different wettability of gold and mica surfaces.

In this study, the microstructure and oxidation behaviour of soot from the raw exhaust of a Euro IV test heavy duty ( HD) diesel engine is investigated and compared to that of spark discharge soot and hexabenzocoronene (HBC, C42H18). We find a microstructure -controlled reactivity toward oxidation of all three samples in 5% O2 in N2. The spark discharge soot with its fine primary particles and fullerenoid structure has an onset temperature of 423 K for combustion, while the hexabenzocoronene with its well-ordered crystallites has a high onset temperature of 773 K. Due to an improved combustion process in the Euro IV HD diesel engine, the soot emitted consists of more fullerenoid-like or onion-like particles agglomerated in a chain-like secondary structure. The onset temperature of the Euro IV HD engine soot combustion is 573 K. Oxidat ion of the three samples produces only CO2 and H2O. The different H2O production profiles can be assigned to the functionalised surface of the samples and depend on the soot structures and preparation route.

The optical absorption and charge transport properties of a series of discotic molecules consisting of peripherally alkyl-substituted polycyclic aromatic cores have been investigated for core sizes, n, of 24, 42, 60, 78, 96, and 132 carbon atoms. In dilute solution, the wavelength maximum of the first absorption band increases linearly with n according to lambda(max) = 280 + 2n and the spectral features become increasingly broadened. The two smallest core compounds display a slight red-shift and increased spectral broadening in spin-coated films. For derivatives with n = 24, 42, 60, and 96, the one-dimensional, intracolumnar charge mobility, Sigma mu(1D), was determined using the pulse-radiolysis time-resolved microwave conductivity technique. For the compounds which were crystalline solids at room temperature, Sigma mu(1D) lay within the range 0.4-1.0 cm(2)/Vs. In the discotic mesophases at ca. 100 degrees C, Sigma mu(1D) was somewhat lower and varied from 0.08 to 0.38 cm(2)/Vs. The mobility values in both phases are considerably larger than the maximum values found previously for discotic triphenylene derivatives. However, the recently proposed trend toward increasing mobility with increasing core size is not substantiated by the results on the present series of increasingly large aromatic core compounds.

Phenylenes are non-benzenoid conjugated -electron systems composed of 6and 4-membered rings, in which no two 6-membered rings are adjacent, and each 4-membered ring is adjacent to two 6-membered rings. The chemistry of phenylenes is in rapid expansion, mainly due to the work of Peter Vollhardt and his research group; for details see the recent papers1,2 and the review.3 To every phenylene it is possible to associate a catacondensed benzenoid system, obtained so that the 4-membered rings of the phenylene are “squeezed off”. This benzenoid system was named4 the hexagonal squeeze of the respective phenylene. The construction of hexagonal squeezes should be evident from the examples depicted in Fig. 1. In the following, a phenylene and its hexagonal squeeze will be denoted by PH and HS, respectively, They possess equal number of hexagons, denoted by h. In the last few years we established a number of nontrivial relations between the topological properties of phenylenes and their hexagonal squeezes.4–12 In the present paper one more such connection is reported. In1984NarumiandKatayama13put forwardanovel toplogical indexSdefinedas

The classical Wiener index, W(G), is equal to the sum of the distances between all pairs of vertexes of a (molecular) graph, G. We now consider a related topological index, pi(G), equal to the product of distances between all pairs of vertexes of G. The basic properties of the pi index are established and its possible physicochemical applications examined. In the case of alkanes, pi and W are highly correlated; a slightly curvilinear correlation exists between In pi and W.

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A discotic polycyclic aromatic hydrocarbon, hexa-peri-hexabenzocoronene, was oriented by slow cooling from the isotropic phase on a water surface as a film. For melt processing at low temperatures, an HBC derivative with long swallow-tailed alkyl side chains was chosen. The supramolecular organization in the resulting thin layer was investigated by electron microscopy. In high-resolution mode, the structural study showed large domains in which the columnar structures were oriented uniaxially with an edge-on arrangement of the hydrophobic molecules. The length of the stacks exceeded several hundred nanometers without obvious defects. The small-area analysis by TEM allowed the direct visualization of individual packed molecules. Electron diffraction revealed a high in-plane order of the columnar superstructures in which the discs were tilted by ca. 40° with respect to the stacking direction. This is the first example of a discotic system melt processed on the water surface yielding a pronounced order.

A window of opportunity: A transparent graphene film has been obtained by a new bottom-up chemical approach involving the thermal reaction of synthetic nanographene molecules of giant polycyclic aromatic hydrocarbons which are cross-linked with each other and further fused into larger graphene sheets. Such graphene films have been applied as window electrodes in organic solar cells (see picture). (Figure Presented).

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Novel polyphenylene-metal complexes with discotic, linear, and dendritic geometries are synthesized by using a facile approach consisting of reactions between Co2(CO)8 and ethynyl functionalities in dichloromethane. Various carbon nanoparticles (CNPs), including graphitic carbon nanotubes (CNTs), graphitic carbon rods, and carbon-metal hybrid particles are obtained from the solid-state pyrolysis of these complexes. The ultimate structures of the CNPs are found to be dependant on the structure and composition of the starting compounds. Precursors containing graphenes always result in graphitic CNTs in high yield, whereas dendritic precursors give rodlike carbon materials. Alternatively, linear oligo(arylethylene) precursors afford mostly carbon-metal hybrids with large amounts of amorphous carbon. Furthermore, the CNP structures could be controlled by adjusting the carbon/metal ratio, the type and position of the metal incorporated into the precursor, and the mode of pyrolysis. These results provide further chances toward understanding the mechanism of CNP formation.

Transient photocurrent measurements were performed for a series of layers of discotic liquid crystals and of perylene derivative prepared in different ways with an aim to characterize the charge carrier transport in configurations corresponding to photovoltaic devices and field effect transistors. The course of the transient photocurrent was found to be strongly dependent on the layer preparation procedure: the non-dispersive transport, and well defined transit times, were found only for “squeezed” sandwich-type sample of triphenylene derivative in which homeotropic orientation of the discotic columns was induced assuring formation of continuous paths connecting the opposite electrodes. In all other cases dispersive transport of charge carriers was observed, due to the spatial and/or energy disorder of hopping states and fast trapping by localized states. From the asymmetry of the transient photocurrents for different polarity of the illuminated electrode it was concluded, that holes are more mobile in the hexabenzocoronene derivatives and in the triphenylene derivative, while electron transport dominates in the perylene derivative.

A magnetic field has been utilized for producing highly oriented films of a substituted hexabenzocoronene (HBC). Optical microscopy studies revealed large area HBC monodomains that covered the entire film, while wide-angle X-ray measurements showed that the HBC molecules are aligned with their planes along the applied field. On the basis of this method, solution-processed field-effect transistors (FET) have been constructed with charge carrier mobilities of up to 10(-3) cm2/V.s, which are significantly enhanced with respect to the unaligned material. Exceptionally high mobility anisotropies of 25-75 for current flow parallel and perpendicular to the alignment direction have been measured as a function of the channel length. Atomic force microscopy performed on the FET structures reveals fibril superstructures that are oriented perpendicularly to the magnetic field direction, consisting of molecular columns with a slippage angle of 40 degrees between the molecules. For channel lengths larger than 2.5 mum, the fibrils are smaller than the electrode spacing, which adversely affects the device performance.

We report a Kelvin-probe force microscopy (KPFM) investigation on the structural and electronic properties of different submicronscale supramolecular architectures of a synthetic nanographene, including extended layers, percolated networks and broken patterm grown from solutions at surfaces. This study made it possible to determine the local work function (WF) of the different π-conjugated nanostructures adsorbed on mica with a resolution below 10 nm and 0.05 eV. It revealed that the WF strongly depends on the local molecular order at the surface, in particular on the delocalization of electrons in the π-states, on the molecular orientation at surfaces, on the molecular packing density, on the presence of defects in the film and on the different conformations of the aliphatic peripheral chains that might cover the conjugated core. These results were confirmed by comparing the KPFM-estimated local WF of layers supported on mica, where the molecules are preferentially packed edge-on on the substrate, with the ultraviolet photoelectron spectroscopy microscopically measured WF of layers adsorbed on graphite, where the molecules should tend to assemble face-on at the surface. It appears that local WF studies are of paramount importance for understanding the electronic properties of active organic nanostructures, being therefore fundamental for the building of high-performance organic electronic devices, including field-effect transistors, light-emitting diodes and solar cells.

Branched hydrocarbon propellers (9 and 12) were prepared by stepwise palladium-catalyzed Hagihara-Sonogashira coupling reactions and Diels-Alder cycloadditions and submitted to oxidative cyclodehydrogenation by FeCl 3 to afford two new giant graphite disks 2 and 3 with 3-fold symmetry in high yield. One of the precursors, the polyphenylene dendrimer 9 containing 150 carbon atoms, was crystallographically characterized. The poorly soluble graphite disks were characterized by isotope-resolved MALDI-TOF mass spectroscopy, and their electronic and vibrational properties were investigated by solid-state UV-vis and Raman spectroscopy. The effect of molecular size and geometry on their properties was discussed. The molecule 2 represents the largest, 3-fold-symmetric all-benzenoid graphite disk, and the five-membered rings in molecule 3 open the opportunity to synthesize large bowl-shaped PAHs.

A new synthetic protocol that affords novel hexa-peri-hexabenzocoronene (HBC) derivatives with partial “zig/zag” periphery and dramatically different electronic properties has been developed, which represents an important step toward understanding structure−property relationships of graphitic materials. The scope of this methodology was broadened by application to a much larger polycyclic aromatic hydrocarbon (PAH) with a more extended “zig/zag” character.

The monolayer formation of a chiral oligo(p-phenylene vinylene)-substituted hexaarylbenzene with 24 stereogenic centers is investigated at the interface between a liquid and a solid substrate, highly oriented pyrolytic graphite. Scanning tunneling microscopy (STM) reveals that molecular chirality is expressed at the supramolecular level. When both enantiomers are co-adsorbed on the surface, a racemic conglomerate is formed. Both enantiomers and their mixtures show interesting conformational and translational dynamics at the liquid-solid interface, giving insight into expression of chirality, nucleation and monolayer growth.