Photo-controllable azobenzene microdroplets on an open surface and their application as transporters.

The control of droplet motion is a significant challenge, as there has been no simple method for effective manipulation. Utilizing light for the control of droplets offers a promising solution due to its non-contact nature and high degree of controllability. In this study, we present our findings on the translational motion of pre-photomelted droplets composed of azobenzene derivatives on a glass surface when exposed to UV and visible light sources from different directions. These droplets exhibited directional and continuous motion upon light irradiation and this motion was size-dependent. Only droplets with diameters less than 10 µm moved with a maximum velocity of 300 µm min-1. In addition, the direction of the movement was controllable by the direction of the light. The motion is driven by a change in contact angle, where UV or visible light switched the contact angle to approximately 50° or 35°, respectively. In addition, these droplets were also found to be capable carriers for fluorescent quantum dots. As such, droplets composed of photoresponsive molecules offer unique opportunities for designing novel light-driven open-surface microfluidic systems.

Two-dimensional molecular networks at the solid/liquid interface and the role of alkyl chains in their building blocks.

Nanoarchitectonics has attracted increasing attention owing to its potential applications in nanomachines, nanoelectronics, catalysis, and nanopatterning, which can contribute to overcoming global problems related to energy and environment, among others. However, the fabrication of ordered nanoarchitectures remains a challenge, even in two dimensions. Therefore, a deeper understanding of the self-assembly processes and substantial factors for building ordered structures is critical for tailoring flexible and desirable nanoarchitectures. Scanning tunneling microscopy is a powerful tool for revealing the molecular conformations, arrangements, and orientations of two-dimensional (2D) networks on surfaces. The fabrication of 2D assemblies involves non-covalent interactions that play a significant role in the molecular arrangement and orientation. Among the non-covalent interactions, dispersion interactions that derive from alkyl chain units are believed to be weak. However, alkyl chains play an important role in the adsorption onto substrates, as well as in the in-plane intermolecular interactions. In this review, we focus on the role of alkyl chains in the formation of ordered 2D assemblies at the solid/liquid interface. The alkyl chain effects on the 2D assemblies are introduced together with examples documented in the past decades.

Analysis of intermolecular interactions of n-perfluoroalkanes with circumcoronene using dispersion-corrected DFT calculations: comparison with those of n-alkanes.

Understanding the interactions between the adsorbate and substrate is critical in basic and advanced scientific fields, including the formation of well-organised nanoarchitectures via self-assembly on surfaces. In this study, the interactions of n-alkanes and n-perfluoroalkanes with circumcoronene were studied using dispersion-corrected density functional theory calculations as models of their adsorption on graphite. The interactions of n-perfluoroalkanes with circumcoronene were significantly weaker than those of the corresponding n-alkanes, e.g. the calculated adsorption energies of n-perfluorohexane and n-hexane were -9.05 and -13.06 kcal mol-1, respectively. The dispersion interactions were the major source of attraction between circumcoronene and the adsorbed molecules. Larger steric repulsion of n-perfluoroalkanes compared to those of n-alkanes increased their equilibrium distances from circumcoronene and decreased the dispersion interactions, resulting in weaker interactions. The interactions between two adsorbed n-perfluorohexane molecules and those of n-hexane molecules were -2.96 and -2.98 kcal mol-1, respectively, which are not negligible in the stabilisation of adsorbed molecules. The geometries of adsorbed n-perfluoroalkane dimers revealed that the equilibrium distance between two n-perfluoroalkane molecules did not match the width of the six-membered rings in circumcoronene, in contrast to that between n-alkanes. The lattice mismatch also destabilised the adsorbed n-perfluoroalkane dimers. The difference in the adsorption energy between flat-on and edge-on orientations of n-perfluorohexane was smaller than that of corresponding n-hexane.

Tuning the odd-even effect on two-dimensional assemblies of curcumin derivatives by alkyl chain substitution: a scanning tunnelling microscopy study.

Well-ordered molecular arrangement on surfaces is fundamental for fabrication of functional molecular devices which are of particular interest in nanotechnology. In addition to nano-manufacturing, the production of useful materials from natural resources has recently attracted increasing attention. Herein, we focused on the two-dimensional (2D) self-assemblies of curcumin derivatives. The effects of the number, length, and substitution of the alkyl chains on the 2D structures of curcumin derivatives were studied by scanning tunnelling microscopy at the highly oriented pyrolytic graphite/1,2,4-trichlorobenzene interface. Curcumin derivatives containing both methoxy and alkoxy chain groups and those possessing four alkoxy chains exhibit linear structures with and without interdigitation of alkoxy chains, respectively. These 2D structure formations are independent of the alkyl chain length. However, the bisdemethoxycurcumin derivatives periodically form stair-like and linear structures depending on the alkyl chain length, which indicates the existence of the odd-even effect. These results suggest that the 2D structural modulation of curcumin derivatives caused by the odd-even effect can be tuned by the number of alkyl chain substituents. The appearance and disappearance of the odd-even effect in curcumin derivatives are discussed in terms of the balance between intermolecular and molecule-substrate interactions.

Molecular Weight-Dependent Oxidation and Optoelectronic Properties of Defect-Free Macrocyclic Poly(3-hexylthiophene).

The redox behaviors of macrocyclic molecules with an entirely π-conjugated system are of interest due to their unique optical, electronic, and magnetic properties. In this study, defect-free cyclic P3HT with a degree of polymerization (DPn) from 14 to 43 was synthesized based on our previously established method, and its unique redox behaviors arising from the cyclic topology were investigated. Cyclic voltammetry (CV) showed that the HOMO level of cyclic P3HT decreases from -4.86 eV (14 mer) to -4.89 eV (43 mer), in contrast to the linear counterparts increasing from -4.94 eV (14 mer) to -4.91 eV (43 mer). During the CV measurement, linear P3HT suffered from electro-oxidation at the chain ends, while cyclic P3HT was stable. ESR and UV-Vis-NIR spectroscopy suggested that cyclic P3HT has stronger dicationic properties due to the interactions between the polarons. On the other hand, linear P3HT showed characteristics of polaron pairs with multiple isolated polarons. Moreover, the dicationic properties of cyclic P3HT were more pronounced for the smaller macrocycles.

Two-dimensional self-assemblies of azobenzene derivatives: effects of methyl substitution of azobenzene core and alkyl chain length.

Elucidating the correlation between the molecular arrangement and physical properties of organic compounds is critical to facilitating the development of advanced functional materials. X-ray structural analyses are generally performed to clarify this relationship. Several attempts have been made to ascertain the links between three-dimensional (3D) crystals and their two-dimensional (2D) structures, which can be revealed by scanning tunnelling microscopy (STM) at the molecular level. Thus, 2D self-assemblies of a series of azobenzene derivatives were investigated in this study, and the effects of methyl substitution of the azobenzene core and alkyl chain length on the 2D molecular arrangements at the solid/liquid interface were revealed. Three types of azobenzene derivatives were prepared; these contained azobenzene (Az), 3-methyl azobenzene (MAz), or 3,3'-dimethyl azobenzene (DAz) as cores and alkyloxy chains of different lengths (C8-13) at their 4,4' positions. The 2D structures of the Az and DAz compounds were found to be modulated owing to the odd-even effect of the alkyl chains in a specific chain-length range; this effect was only weakly exhibited by the MAz compounds. This result suggests that only the methyl-group substitution of the azobenzene core significantly affected the 2D structures. The 2D structural features have been discussed in terms of molecular conformation, as well as their correlation with the photo-melting behaviour of the azobenzene derivatives, particularly the MAz compounds.

Halogen bond-directed self-assembly in bicomponent blends at the solid/liquid interface: effect of the alkyl chain substitution position.

The fabrication of well-organised molecular assemblies on surfaces is fundamental for the creation of functional molecular systems applicable to nanoelectronic and molecular devices. In this study, we investigated the effect of substitution positions of alkyl chains on the formation of halogen-bonded molecular networks. For this purpose, building blocks with different head groups (i.e., pyridine (Py) or tetrafluoro-iodobenzene (FI)) were substituted with hexadecyloxy chains at either the 3,4- or the 3,5-positions. The two-dimensional assembly of each compound as a single-component system was studied using scanning tunnelling microscopy (STM) at the highly oriented pyrolytic graphite (HOPG)/1-phenyloctane interface. All compounds displayed linear structures in which the alkyl chains were aligned along one of the HOPG axes. In the exceptional case of FI bearing hexadecyloxy chains at the 3,5-positions (denoted as FI-3,5), hexagonal arrays were tentatively formed owing to the triangular molecular arrangement induced by halogen bonding. A bicomponent blend of Py-3,4/FI-3,5 (1 : 1 molar ratio) enabled the formation of a honeycomb structure, whereas that of Py-3,5/FI-3,4 (1 : 1 molar ratio) produced a rectangular assembly that was periodically arranged in a zig-zag fashion. Finally, based on the observed blend ratio dependence, the formation of these different two-dimensional structures by variation in the substitution positions of the alkyl chains was discussed in terms of molecule-molecule and molecule-substrate interactions.

Well-organised two-dimensional self-assembly controlled by in situ formation of a Cu(II)-coordinated rufigallol derivative: a scanning tunnelling microscopy study.

The two-dimensional self-assembly of rufigallol derivatives and their metal coordination were studied by scanning tunnelling microscopy. Ex situ Cu(II)-coordinated rufigallol derivatives exhibited columnar structures with some defects, whereas regular and linear structures were formed upon in situ metal coordination at solid/liquid interfaces.

Photo-Induced Crawling Motion of Azobenzene Crystals on Modified Gold Surfaces.

Photo-induced crawling motion of a crystal of 3,3'-dimethylazobenzene (DMAB) on gold surfaces having different surface properties and various patterns was studied. DMAB crystals crawl continuously when exposed to UV and visible lights simultaneously from different directions. On a gold surface functionalized by a thiol having a hydroxyl group at the terminal (16-hydroxy-1-hexadecanethiol (HOC16SH)), the crystals crawled with a relatively high velocity (ca. 4 µm min-1), and they changed the crystal shape while keeping a distinct crystal face. On a gold surface functionalized by a thiol having an alkyl chain terminal (1-hexadecanethiol (C16SH)), the crawling was observed with a slower velocity (ca. 1.5 µm min-1). However, the shape of the crystals became a droplet-like shape soon after the irradiation started, and the shape persisted during the motion. Light intensity dependence of the crawling velocity of the droplet-like crystal on this surface showed that UV light has stronger dependence for the motion than the visible light. On a substrate with a stripe pattern of alternating C16SH-modified gold and hexadecyltrimethylsilane (HDTMS)-modified glass, crystals crawled only on the surface of the C16SH-modified gold, which may be due to the wettability hysteresis at the surface. On a substrate with a stripe pattern of HOC16SH-modified gold and HDTMS-modified glass, crystals were attracted to the gold side. On a gold substrate with a periodic pattern of different height (ca. 50 nm) but having a uniform treatment with C16SH, crystals crawled up and down the steps without significant disturbance at the boundary of the step. Therefore, wettability of the surface has a greater impact on controlling the motion of the crystal than the surface structure. The present results not only unveil the crawling behavior on various surfaces but also offer a guide to controlling the motion toward applications for novel carriage vehicles to transport molecules/objects on a surface.

Effect of Surface Properties on the Photo-Induced Crawling Motion of Azobenzene Crystals on Glass Surfaces.

Photo-induced crawling motion of a crystal of 3,3'-dimethylazobenzene (DMAB) on a glass substrate having different surface properties was studied. When exposed to UV and visible lights simultaneously from different directions, crystals crawl continuously on a glass surface. On a hydrophilic surface, the crystals crawled faster than those on other surfaces but crystals showed spreading while they moved. On hydrophobic surfaces, on the other hand, the crystals showed little shape change and slower crawling motion. The contact angles of the liquid phase of DMAB on surface-modified glass substrates showed positive correlation with the water contact angles. The interaction of melted azobenzene with glass surfaces plays an important role for the crawling motion. We proposed models to explain the asymmetric condition that leads to the directional motion. Specifically by considering the penetration length of UV and visible light sources, it was successfully shown that the depth of light penetration is different at the position of a crystal. This creates a nonequilibrium condition where melting and crystallization are predominant in the same crystal.

Dynamic host-guest behavior in halogen-bonded two-dimensional molecular networks investigated by scanning tunneling microscopy at the solid/liquid interface.

The fabrication of supramolecularly engineered two-dimensional (2D) networks using simple molecular building blocks is an effective means for studying host-guest chemistry at surfaces toward the potential application of such systems in nanoelectronics and molecular devices. In this study, halogen-bonded molecular networks were constructed by the combination of linear halogen-bond donor and acceptor ligands, and their 2D structures at the highly oriented pyrolytic graphite/1-phenyloctane interface were studied by scanning tunneling microscopy. The bi-component blend of the molecular building blocks possessing tetradecyloxy chains formed a lozenge structure via halogen bonding. Upon the introduction of an appropriate guest molecule (e.g., coronene) into the system, the 2D structure transformed into a hexagonal array, and the central pore of this array was occupied by the guest molecules. Remarkably, the halogen bonding of the original structure was maintained after the introduction of the guest molecule. Thus, the halogen-bonded molecular networks are applicable for assembling guest species on the substrate without the requirement of the conventional rigid molecular building blocks with C 3 symmetry.

Coordination-Driven Construction of Porphyrin Nanoribbons at a Highly Oriented Pyrolytic Graphite (HOPG)/Liquid Interface.

Nanostructures were built at the solid/liquid interface by self-assembly and/or coordination bonds. Metalloporphyrins bearing two external coordination sites and long alkyl chains allowed the self-assembly of the compounds on highly oriented pyrolitic graphite. After addition of a metal ion, long transition-metal linked porphyrin nanoribbons were obtained and visualized by scanning tunneling microscopy. In these porphyrin ribbons electronic delocalization is possible through the d orbitals of the connecting metal ions.

Hexagonal array formation by intermolecular halogen bonding using a binary blend of linear building blocks: STM study.

Hexagonal arrays were fabricated via intermolecular halogen bonding between two linear molecular building blocks in a bicomponent blend. The substitution position of the pyridine N atom involved in the halogen bond plays an important role in the formation of the hexagonal structures.

Synthesis and Study at a Solid/Liquid Interface of Porphyrin Dimers Linked by Metal Ions.

Several porphyrin dimers linked by metal ions were prepared. One trimeric compound was also isolated and one porphyrin dimer linked by palladium(II) could be structurally characterized. In solution, the size of the new compounds was estimated by DOSY NMR techniques. These compounds all contained long aliphatic chains (O-C12H25), which were used to assemble them at a highly oriented pyrolytic graphite (HOPG)/liquid interface. The highly ordered arrays were visualized by scanning tunneling microscopy (STM).

Odd-even effect in two dimensions induced by the bicomponent blends of isobutenyl compounds.

Scanning tunneling microscopy (STM) investigation was performed for the blends of isobutenyl compounds, in which the long alkyl chains were connected with ester or carbamoyl linkages. Each component by itself did not show the odd-even effect of alkyl chain length, whereas after blending them, the 2D structures drastically changed and modulated to exhibit odd-even effect. Star, lozenge, twist-like, and linear structures were found, dependent on the blend ratio and alkyl chain length. The blend ratio dependence of 2D structures was explained in terms of homogeneous and heterogeneous dimerization due to the interdigitation of alkyl chains.

High-fidelity self-assembly pathways for hydrogen-bonding molecular semiconductors.

The design of molecular systems with high-fidelity self-assembly pathways that include several levels of hierarchy is of primary importance for the understanding of structure-function relationships, as well as for controlling the functionality of organic materials. Reported herein is a high-fidelity self-assembly system that comprises two hydrogen-bonding molecular semiconductors with regioisomerically attached short alkyl chains. Despite the availability of both discrete cyclic and polymeric linear hydrogen-bonding motifs, the two regioisomers select one of the two motifs in homogeneous solution as well as at the 2D-confined liquid-solid interface. This selectivity arises from the high directionality of the involved hydrogen-bonding interactions, which renders rerouting to other self-assembly pathways difficult. In thin films and in the bulk, the resulting hydrogen-bonded assemblies further organize into the expected columnar and lamellar higher-order architectures via solution processing. The contrasting organized structures of these regioisomers are reflected in their notably different miscibility with soluble fullerene derivatives in the solid state. Thus, electron donor-acceptor blend films deliver a distinctly different photovoltaic performance, despite their virtually identical intrinsic optoelectronic properties. Currently, we attribute this high-fidelity control via self-assembly pathways to the molecular design of these supramolecular semiconductors, which lacks structure-determining long aliphatic chains.

Trapping Nanostructures on Surfaces through Weak Interactions.

The assembly of imidazole-functionalized phenanthroline-strapped zinc porphyrins (ZnPorphen) with alkyl or polyethylene glycol (PEG) side chains was studied in solution and by AFM after casting on highly oriented pyrolytic graphite (HOPG) or mica. The nature of the solvent and its evaporation time influenced the morphology of the objects observed. On HOPG, short rods of about 100 nm were observed after fast evaporation of solutions of the alkyl derivatives in CHCl3 , THF, or pyridine, whereas islands of aligned rows of longer wires were obtained from methylcyclohexane (MCH). Slow evaporation of MCH led to a three-dimensional assembly. The PEG porphyrin assembled into short wires on HOPG or fibers on mica after slow evaporation of solutions in THF. This study shows the role of surface-molecule interactions in the interfacial assembly of ZnPorphen derivatives and contributes to understanding the parameters that control their noncovalent assembly into molecular wires on a surface.

Supramolecular engineering of oligothiophene nanorods without insulators: hierarchical association of rosettes and photovoltaic properties.

Supramolecular rosettes of oligothiophenes that do not bear long aliphatic tails have been designed as semiconducting nanomaterials for solution-processable bulk heterojunction solar cells. The rosettes consist of six barbiturated thienyl[oligo(hexylthiophene)] units (Bar-T-hTn ; n=3,4,5) aggregated by multiple hydrogen bonds, which have been directly visualized by scanning tunneling microscopy (STM) at a solid-liquid interface. (1) H NMR spectroscopy in [D8 ]toluene showed that Bar-T-hTn exists as a mixture of monomers and small hydrogen-bonded aggregates. Hierarchical organization of the hydrogen-bonded aggregates took place through π-π stacking interactions upon casting their toluene solutions, resulting in the growth of highly ordered nanorods whose widths are consistent with the diameters of the rosettes. The nanorods could be generated in the presence of soluble fullerene derivatives via solution casting or the annealing of the resulting thin films. The solar cells fabricated based on these bulk heterojunction films showed power conversion efficiencies of 1-3 %, which are far higher than those of the non-hydrogen-bonded reference oligothiophene and the derivative that possesses long aliphatic tails.

Bicomponent blend-directed amplification of the alkyl chain effect on the 2D structures.

Only one methylene unit difference in the long alkyl group of isobutenyl ether compounds is amplified by blending, resulting in the diversification of 2D structures, although each component formed individual 2D patterns, regardless of alkyl chain lengths. The 2D structures were revealed by using scanning tunneling microscopy at the solid/liquid interface.