Rational molecular design and processing, enabling large-area molecular ordering, are important for creating high-performance organic materials and devices. We show that, upon one-step hot pressing with uniaxially stretched Teflon sheets, a polymer brush carrying azobenzene-containing mesogenic side chains self-assembles into a free-standing film, where the polymer backbone aligns homeotropically to the film plane, and the side chains align horizontally. Such an ordered structure forms through translation of a one-dimensional molecular order of the Teflon sheet and propagates from the interface macroscopically on both sides of the film. The resultant wide-area bimorph configuration allows the polymer film to bend rapidly and reversibly when the azobenzene units are photoisomerized. The combination of polymer brushes with hot pressing and Teflon sheets provides many possibilities in designing functional soft materials.

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Donor-substituted alkynes and electron-accepting olefins undergo a formal [2+2]cycloaddition, followed by retro-electrocyclization, under formation of non-planar D-p-A chromophores. The transformations are typical "click-chemistry"-type reactions: high-yielding, atom-economic, and in most cases very rapid. Despite their pronounced non-planarity, the resulting chromophores feature efficient intramolecular CT interactions, show high third-order optical nonlinearities. We also achieved multiple cascades of the click reaction yielding chromophores with strong optical absorptions spanning the entire visible light wavelength. The new chromophores remain potent electron acceptors and can even be classified as "super acceptors". Lately, we demonstrated that efficient push-pull conjugation also occurs in homoconjugated and spiroconjugated systems. We conjugated these push-pull chromophores to fullerenes and observed unprecedented rearrangements on the carbon sphere. Axial chirality is enforced in push-pull substituted buta-1,3-dienes, conjugated to C60, by a single alkyl group on the surface. In the second part, synthesis and characterization of unprecedented chiral, alleno-acetylenic chromophores with all-carbon backbones, composed of 1,3-diethynylallene repeat units, is presented. Optically active alleno-acetylenic macrocycles were obtained featuring exceptionally intense Cotton effects. Unprecedented amplification of chirality is observed in monodisperse, enantiomerically pure alleno-acetylenic oligomers. Despite the steric protection of the delicate allene moiety, intramolecular transformations can be established, such as Diels-Alder cycloadditions and allenyl-Cope rearrangements.

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This lecture highlights elements of our efforts to explore new synthetic chemistry of nanocarbons, such as fullerenes, carbon nanorings, carbon nanotubes, and nanographenes, using molecular catalysts.

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The molecular surgical approach, involving creation of an orifice on the empty fullerene cage, insertion of a small guest through the orifice, and closure of the orifice with retention of the guest, is a promising method to synthesize yet-unknown endohedral fullerenes. Herein wereport the synthesis of H2O@C60 with dynamic control of the orifice-size under mild conditions as well as application of open-cage C60 derivatives to organic photovoltaic devices.

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We developed a saccharide introduced low molecular weight hydrogelator that showed gel-sol transition based on molecular recognition. This study, we designed a amphiphilic molecule having hydroxyl groups as simple hydrophilic moiety. The amphiphilic molecule showed better gelation ability and pH reversible-gelation. Furthermore, simple modification of this hydroxyl groups with alkyl chain enabled to convert into a low molecular weight organogelator for organic solvent.

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Pyridazinediols annulated tetrathiafulvalenes with hydrogen bonding sites and pi-pi stacking unit form various aggregates depending on solvents, temperature, concentration and so on. We previously reported that pylidazinediols annulated TTF derivatives with long alkyl chains form fibrous structure from common organic solvents. In this time, we found that derivatives with methylthio group (1) formed supramolecular gel from dimethyl sulfoxide-methanol solution containing hydrazine molecules. Additionally, the gel transformed into pseudo-polymorphic single crystals spontaneously at room temperature. In this presentation, we wish to present the details and its structure control.

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Recently, nanofibers based on -conjugated molecules have been paid attention from the viewpoint of application for new organic electronics materials. For improvement of their carrier mobility, their crystallinity is very important. To achieve high crystallinity nanofibers, three dehydrobenzoannulene (DBA) derivatives without long alkyl chains were designed and synthesized based on the novel strategy which we proposed. The three DBA derivatives constructed high crystalline nanofibers. In this presentation, we describe molecular arrangements and properties of the nanofibers.

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We prepared and characterized donor-type self-assembled monolayers (SAMs) to apply n-type organic field effect transistors (OFET). We have designed and synthesized a series of tetrathiafulvalene derivatives fused to benzene, 1,4-dithiane and 1,4-dioxane having triethoxysilyl groups as an anchor unit to prepare the self-assembled monolayers (SAMs) possessing charge transfer ability. The layer properties of SAMs on the silicon dioxide covered with these compounds were fully characterized by X-ray photoelelectron spectroscopy (XPS) and water contact angle (WCA). The OFET characteristics modified by the SAM and cupper hexadecafluorophthalocyanine as a semiconducting layer will be discussed in the presentation.

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Achievement of a self-reproducing giant vesicle (GV) consisting of a synthesized cationic membrane molecule, its cationic bolaamphiphilic precursor, and an acidic amphiphilic catalyst, and self-replication of an informational molecule (DNA) in a non-self-reproducing GV through a polymerase chain reaction promoted us to link the self-replication of DNA in a GV and self-reproduction of the GV chemically. We found that an addition of the membrane precursor to a dispersion of GVs with amplified DNA caused a series of rapid growth-and-division processes of GVs made of phospholipids containing the cationic membrane molecule and the catalyst. It is suspected that the adhesion of some of the amplified DNA to an inner surface of the outer vesicular membrane assists the formation of the membrane molecule from its precursor. Since the amplified DNA was partitioned to the newly formed GVs, this vesicular system can be regarded as a chemically constructed primitive protocell.

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