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The assembly of donor–acceptor molecules via charge transfer (CT) interactions gives rise to highly ordered nanomaterials with appealing electronic properties. Here, we present the synthesis and bulk co-assembly of pyrene (Pyr) and naphthalenediimide (NDI) functionalized oligodimethylsiloxanes (oDMS) of discrete length. We tune the donor–acceptor interactions by connecting the pyrene and NDI to the same oligomer, forming a heterotelechelic block molecule (NDI-oDMSPyr), and to two separate oligomers, giving Pyr and NDI homotelechelic block molecules (Pyr-oDMS and NDI-oDMS). Liquid crystalline materials are obtained for binary mixtures of Pyr-oDMS and NDI-oDMS, while crystallization of the CT dimers occurred for the heterotelechelic NDI-oDMS-Pyr block molecule. The synergy between crystallization and phase-segregation coupled with the discrete length of the oDMS units allows for perfect order and sharp interfaces between the insulating siloxane and CT layers composed of crystalline CT dimers. We were able to tune the lamellar domain spacing and donor–acceptor CT interactions by applying pressures up to 6 GPa on the material, making the system promising for soft-material nanotechnologies. These results demonstrate the importance of the molecular design to tune the CT interactions and stability of a CT material., A robust, soft material held together by charge transfer interactions is developed. The nanostructure dimensions and material properties can be tuned by molecular design or pressure.

We developed a photoreactive molecular glue, BPGlue-N3, which can provide a universal strategy to enhance the efficacy of DNA aptamers by temporary-to-permanent stepwise stabilization of their conjugates with target proteins. As a proof-of-concept study, we applied BPGlue-N3 to the SL1 (DNA aptamer)/c-Met (target protein) conjugate system. BPGlue-N3 can adhere to and temporarily stabilize this aptamer/protein conjugate multivalently using its guanidinium ion (Gu+) pendants that form a salt bridge with oxyanionic moieties (e.g., carboxylate and phosphate) and benzophenone (BP) group that is highly affinitive to DNA duplexes. BPGlue-N3 is designed to carry a dual-mode photoreactivity; upon exposure to UV light, the temporarily stabilized aptamer/protein conjugate reacts with the photoexcited BP unit of adhering BPGlue-N3 and also a nitrene species, possibly generated by the BP-to-N3 energy transfer in BPGlue-N3. We confirmed that SL1, covalently conjugated with c-Met, hampered the binding of hepatocyte growth factor (HGF) onto c-Met, even when the SL1/c-Met conjugate was rinsed prior to the treatment with HGF, and suppressed cell migration caused by HGF-induced c-Met phosphorylation.

Although various biomimetic soft materials that display structural hierarchies and stimuli responsiveness have been developed from organic materials, the creation of their counterparts consisting entirely of inorganic materials presents an attractive challenge, as the properties of such materials generally differ from those of living organisms. Here, we have developed a hydrogel consisting of inorganic nanosheets (14 wt%) and water (86 wt%) that undergoes thermally induced reversible and abrupt changes in its internal structure and mechanical elasticity (23-fold). At room temperature, the nanosheets in water electrostatically repel one another and self-assemble into a long-periodic lamellar architecture with mutually restricted mobility, forming a physical hydrogel. Upon heating above 55 °C, the electrostatic repulsion is overcome by competing van der Waals attraction, and the nanosheets rearrange into an interconnected 3D network of another hydrogel. By doping the gel with a photothermal-conversion agent, the gel-to-gel transition becomes operable spatiotemporally on photoirradiation., Inorganic soft materials are an attractive concept but challenging to make. Here the authors have developed a hydrogel consisting of inorganic nanosheets (14 wt%) and water (86 wt%) that undergoes thermally induced reversible and abrupt changes in its internal structure and mechanical elasticity (23-fold).

Significance As the formation of quasicrystalline ordering in both metal alloys and soft matters reinforces the scale-invariance principle, however, it remains unknown that why metallic quasicrystals prefer decagonal quasicrystalline (DQC, 10-fold) ordering, and the condensed soft maters only exhibit dodecagonal quasicrystalline (DDQC, 12-fold) ordering. By tuning the self-sorting ability in a pair of giant molecules, the well-mixed binary blends generate a metastable DQC phase and corresponding unprecedent phase sequence (DQC → DDQC → Frank–Kasper σ) during thermal annealing. These peculiar assembling behaviors result from interplays of submesoatomic and mesoatomic packings. Reducing the self-sorting strength has induced an extra complexity in the sub-mesoatomic packings of giant molecules, which further influences the clustering on the mesoatomic level., The quasiperiodic structures in metal alloys have been known to depend on the existence of icosahedral order in the melt. Among different phases observed in intermetallics, decagonal quasicrystal (DQC) structures have been identified in many glass-forming alloys yet remain inaccessible in bulk-state condensed soft matters. Via annealing the mixture of two giant molecules, the binary system assemblies into an axial DQC superlattice, which is identified comprehensively with meso-atomic accuracy. Analysis indicates that the DQC superlattice is composed of mesoatoms with an unusually broad volume distribution. The interplays of submesoatomic (molecular) and mesoatomic (supramolecular) local packings are found to play a crucial role in not only the formation of the metastable DQC superlattice but also its transition to dodecagonal quasicrystal and Frank–Kasper σ superlattices.

Although chirality has been recognized as an essential entity for life, it still remains a big mystery how the homochirality in nature emerged in essential biomolecules. Certain achiral motifs are known to assemble into chiral nanostructures. In rare cases, their absolute geometries are enantiomerically biased by mirror symmetry breaking. Here we report the first example of asymmetric catalysis by using a mirror symmetry-broken helical nanoribbon as the ligand. We obtain this helical nanoribbon from a benzoic acid appended achiral benzene-1,3,5-tricarboxamide by its helical supramolecular assembly and employ it for the Cu2+-catalyzed Diels–Alder reaction. By thorough optimization of the reaction (conversion: > 99%, turnover number: ~90), the enantiomeric excess eventually reaches 46% (major/minor enantiomers = 73/27). We also confirm that the helical nanoribbon indeed carries helically twisted binding sites for Cu2+. Our achievement may provide the fundamental breakthrough for producing optically active molecules from a mixture of totally achiral motifs., If asymmetric catalysts were available by mirror symmetry breaking, an important insight may be given to how the biomolecular homochirality emerged in nature. Here, the authors report the first example of asymmetric catalysis by employing mirror symmetry-broken helical nanoribbons as the ligand.

The research field of supramolecular polymerization has dramatically progressed in the last three decades, and much deeper insights into its new mechanisms, including kinetic and thermodynamic aspects, have become available. Furthermore, a much wider variety of noncovalent interactions have been exploited for connecting monomers, and the importance of multivalency and the concept of pathway complexity have also been recognized. To control supramolecular polymerization, chain-growth supramolecular polymerization, seeded supramolecular polymerization, and sequence-specific supramolecular copolymerization, which are essential for precise macromolecular synthesis, are now possible. The stereochemical aspects of supramolecular polymerization using chiral monomers have also been studied extensively, contributing to the understanding of the kinetic aspects of supramolecular polymerization. Nanotubular supramolecular polymerization, forming rolled-up 2D architectures, in contrast to linear supramolecular polymerization, has also been developed. Through the conceptual expansion of supramolecular polymerization, a much wider variety of monomers and media have become usable, which will enable many groundbreaking applications that cannot be attained by conventional covalent polymerization.

For the concept of aromaticity, energetic quantification is crucial. However, this has been elusive for excited-state (Baird) aromaticity. Here we report our serendipitous discovery of two nonplanar thiophene-fused chiral [4n]annulenes Th4 COT Saddle and Th6 CDH Screw, which by computational analysis turned out to be a pair of molecules suitable for energetic quantification of Baird aromaticity. Their enantiomers were separable chromatographically but racemized thermally, enabling investigation of the ring inversion kinetics. In contrast to Th6 CDH Screw, which inverts through a nonplanar transition state, the inversion of Th4 COT Saddle, progressing through a planar transition state, was remarkably accelerated upon photoexcitation. As predicted by Baird’s theory, the planar conformation of Th4 COT Saddle is stabilized in the photoexcited state, thereby enabling lower activation enthalpy than that in the ground state. The lowering of the activation enthalpy, i.e., the energetic impact of excited-state aromaticity, was quantified experimentally to be as high as 21–22 kcal mol–1., Baird’s rule applies to cyclic π-conjugated molecules in their excited state, yet a quantification of the involved energetics is elusive. Here, the authors show the ring inversion kinetics of two nonplanar and chiral [4n]annulenes to support Baird’s rule from an energetic point of view.

Brilliance usually refers to the light reflected by the facets of a gemstone such as diamond due to its high refractive index. Nowadays, high-refractive-index materials find application in many optical and photonic devices and are mostly of inorganic nature. However, these materials are usually obtained by toxic or expensive production processes. Herein, the synthesis of a thin-film organic semiconductor, namely, polymeric carbon nitride, by thermal chemical vapor deposition is presented. Among polymers, this organic material combines the highest intrinsic refractive index reported so far with high transparency in the visible spectrum, even reaching the range of diamond. Eventually, the herein presented deposition of high quality thin films and their optical characteristics open the way for numerous new applications and devices in optics, photonics, and beyond based on organic materials.

We present an innovative method for the synthesis of boron carbon nitride thin film materials in a simple furnace setup, using commonly available solid precursors and relatively low temperature compared to previous attempts. The as-prepared structural and optical properties of thin films are tuned via the precursor content, leading to a sp2-conjugated boron nitride–carbon nitride mixed material, instead of the commonly reported boron nitride–graphene phase segregation, with tunable optical properties such as band gap and fluorescence.

How to orient polymers homeotropically in thin films has been a long-standing issue in polymer science because polymers intrinsically prefer to lie down. Here we provide a design principle for polymers that are processable into a 2D homeotropic order. The key to this achievement was a recognition that cylindrical polymers can be designed to possess oppositely directed local dipoles in their cross-section, which possibly force polymers to tightly connect bilaterally, affording a 2D rectangular assembly. With a physical assistance of the surface grooves on Teflon sheets that sandwich polymer samples, homeotropic ordering is likely nucleated and gradually propagates upon hot-pressing towards the interior of the film. Consequently, the 2D rectangular lattice is constructed such that its b axis (side chains) aligns along the surface grooves, while its c axis (polymer backbone) aligns homeotropically on a Teflon sheet. This finding paves the way to molecularly engineered 2D polymers with anomalous functions., Vertical alignment of polymers on surfaces is challenging due to their flexibility and tendency to arrange on horizontal planes. Here, the authors report a design principle allowing polymers to be arranged into 2D homeotropic orientations by using long-range dipole-dipole interactions and hot-pressing on Teflon sheets.

One-dimensionally connected organic nanostructures with dissimilar semiconducting properties are expected to provide a reliable platform in understanding the behaviors of photocarriers, which are important for the development of efficient photon-to-electrical energy conversion systems. Although bottom-up supramolecular approaches are considered promising for the realization of such nanoscale heterojunctions, the dynamic nature of molecular assembly is problematic. We report a semiconducting nanoscale organic heterojunction, demonstrated by stepwise nanotubular coassembly of two strategically designed molecular graphenes. The dissimilar nanotubular segments, thus connected noncovalently, were electronically communicable with one another over the heterojunction interface and displayed characteristic excitation energy transfer and charge transport properties not present in a mixture of the corresponding homotropically assembled nanotubes.

We performed kinetic study on the photoconductivity of coassembled nanotubes consisting of an amphiphilic hexa-peri-benzocoronene (HBC) and a HBC derivative appended with an electron-accepting trin...

On the other hand, for exploiting moleculardevices that can self-repair elaborate functions, differentproblems may be encountered that originate from muchsmaller size regimes. For example, design of self-repairableoptoelectronic devices, which are potentially important forsensor and display applications

In the previous papers, we have reported the first dry actuator that can be fabricated simply by layer-by-layer casting, using ‘bucky gel’, a gelatinous room-temperature ionic liquid (IL) containing single-walled carbon nanotubes (SWNTs). In this paper, the electromechanical and electrochemical properties of the bucky-gel actuators composed of the bucky-gel electrode and the gel electrolyte layers containing seven kinds of internal ILs were studied for exploring the details of the actuation mechanism. We measured the frequency dependence of the displacement response of the bucky-gel actuator and it can be successfully simulated by the electrochemical kinetic model. From the simulated result for the frequency dependence of the electromechanical response of the bucky-gel actuators, we determined two parameters for the simulation, the generated strain at a limit of low frequency and the time constant. The time constant was represented by the equivalent circuit composed of series combination of the ionic resistance R, the double-layer capacitance C and the electrode resistance Rel. The IL-dependence of the time constant was determined by that of the ionic resistance R of the gel electrolyte layer. The generated strain at a limit of low frequency is considered to be related to the electromechanical mechanism of the bucky-gel actuator. From their dependence on the IL species and the theoretical modeling reported in the previous papers, we conclude that both the steric repulsion effect due to the transfer of ions to the electrode and ‘the charge injection’ give the bending motion of the bucky-gel actuator. The volume-changes of the cathode and anode change according to the sizes of the cation and anion, respectively. The ion size gives the dependence of the bending motion of the bucky-gel actuator on the internal ionic species.

By using an ionic liquid of 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide, we uniformly dispersed single-walled carbon nanotubes (SWNTs) as chemically stable dopants in a vinylidene fluoride-hexafluoropropylene copolymer matrix to form a composite film. We found that the SWNT content can be increased up to 20 weight percent without reducing the mechanical flexibility or softness of the copolymer. The SWNT composite film was coated with dimethyl-siloxane–based rubber, which exhibited a conductivity of 57 siemens per centimeter and a stretchability of 134%. Further, the elastic conductor was integrated with printed organic transistors to fabricate a rubberlike active matrix with an effective area of 20 by 20 square centimeters. The active matrix sheet can be uniaxially and biaxially stretched by 70% without mechanical or electrical damage. The elastic conductor allows for the construction of electronic integrated circuits, which can be mounted anywhere, including arbitrary curved surfaces and movable parts, such as the joints of a robot's arm.

In a previous paper, we reported the first dry actuator that can be fabricated simply by layer-by-layer casting, using ‘bucky gel’, a gelatinous room-temperature ionic-liquid containing single-walled carbon nanotubes (SWNTs). Our actuator has a bimorph configuration with a polymer-supported internal ionic-liquid electrolyte layer sandwiched by two polymer-supported bucky-gel electrode layers, which allows quick and long-lived operation in air at low applied voltages. In this paper, we propose a new two-step process using a ball-mill method for preparing the casting solution for the bucky-gel electrode in order to improve the performance of the actuator by developing the bucky-gel electrode layer with a high content of SWNTs which are well dispersed in the electrode layer. We measured the displacement and the blocking force of the new bucky-gel actuator fabricated by hot-pressing the prepared electrode and electrolyte layers and analyzed its experimental results by the tri-layer polymer actuator model which was developed by Alici et al. for conducting polymer actuators. We developed the low-voltage driven solid-state actuator that shows the maximum stress and the strain of 4.7 MPa and 1.9%, respectively, which are comparable with any other low-voltage driven solid-state electroactive polymer actuator technology to our knowledge. The advantage of our bucky-gel actuator is not only in its good performance but also in its easy process in fabrication. The present development provides an important step for electromechanical polymer actuator technologies.

Thirteen different hexa-peri-hexabenzocoronenes (HBCs) I-III were newly synthesized, and their self-assembling behaviors were investigated. Taking into account also the reported behaviors of amphiphilic HBCs, some structural parameters of HBC essential for the tubular assembly were revealed. Points to highlight include (1) the importance of two phenyl groups attached to one side of the HBC unit, (2) essential roles of long paraffinic side chains on the other side of the phenyl groups, and (3) no necessity of hydrophilic oligo(ethylene glycol) side chains. The hierarchical nanotubular structure, rendered by virtue of a synchrotron radiation technique, was virtually identical to our previous proposal, where the nanotubes are composed of helically coiled bilayer tapes with a tilting angle of approximately 45 degrees. Each tape consists of pi-stacked HBC units, where the inner and outer HBC layers are connected by interdigitation of paraffinic side chains. The coiled structure is most likely caused by a steric congestion of the phenyl groups attached to the HBC unit, whose tilting direction may determine the handedness of the helically chiral nanotube.

A crystal structure of the racemic form of chiral molecular scissors 1 with a trans configuration at the azobenzene unit (rac-trans-1), in which the scissors adopt a closed geometry with two blade phenyl groups that overlap each other, was successfully determined. X-ray crystallographic determination of the structure of (1S,1'S)-10, which is a derivative of the key precursor of trans-1, was also successful. On the basis of the crystal structure of (1S,1'S)-10, the absolute configuration of 1 and related molecular machines, such as molecular pedal 2, and self-locking rotor 3, which all contain a chiral tetrasubstituted ferrocene module, were determined. A correlation between the absolute configuration and the circular dichroism properties of these molecular machines and their synthetic precursors was also determined.

Helical nanostructures have attracted continuous attention, not only as media for chiral recognition and synthesis, but also as motifs for studying intriguing physical phenomena that never occur in centrosymmetric systems. To improve the quality of signals from these phenomena, which is a key issue for their further exploration, the most straightforward is the macroscopic orientation of helices. Here as a versatile scaffold to rationally construct this hardly accessible structure, we report a polymer framework with helical pores that unidirectionally orient over a large area (∼10 cm2). The framework, prepared by crosslinking a supramolecular liquid crystal preorganized in a magnetic field, is chemically robust, functionalized with carboxyl groups and capable of incorporating various basic or cationic guest molecules. When a nonlinear optical chromophore is incorporated in the framework, the resultant complex displays a markedly efficient nonlinear optical output, owing to the coherence of signals ensured by the macroscopically oriented helical structure., Helical nanostructures often exhibit intriguing physical phenomena. Here, the authors fabricate a helical porous material exhibiting both controlled handedness and macroscopic orientation, which promises applications in a wide array of disciplines.

Self-assembly of a Gemini-shaped, chiral amphiphilic hexa- peri -hexabenzocoronene having two chiral oxyalkylene side chains, along with two lipophilic side chains, yields graphitic nanotubes with one-handed helical chirality. The nanotubes are characterized by an extremely high aspect ratio of >1,000 and have a uniform diameter of 20 nm and a wall thickness of 3 nm. The nanotubes with right- and left-handed helical senses were obtained from the ( S )- and ( R )-enantiomers of the amphiphile, respectively, due to an efficient translation of point chirality into supramolecular helical chirality. The ( S )- and ( R )-enantiomers coassemble at varying mole ratios to give nanotubes, whose circular dichroism profiles are almost unchanged over a wide range of the enantiomeric excess of the amphiphile (100–20%). The high level of chirality amplification thus observed indicates a long-range cooperativity in the self-assembling process. In sharp contrast, a hexabenzocoronene amphiphile with chiral lipophilic side chains did not form nanotubular assemblies. The present work demonstrates the majority rule in noncovalent systems and also may provide a synthetic strategy toward realization of molecular solenoids.

Tetrafluoroborate ion (BF(4)(-)) serves as a powerful and better-behaved promoter than fluoride ion (F(-)) for hydrolytic condensation of alkoxysilanes, such as tetraethoxy orthosilicate, in aqueous media containing amphiphiles with onium ion headgroups as templates, affording thermally and hydrothermally stable mesoporous silica. According to (19)F NMR spectral profiles, BF(4)(-) is localized on a positive-charged micellar surface, thereby allowing a site-selective growth of the silica framework. The resulting porous silica has an ordered hexagonal structure with a well-developed and thick silicate wall. Even without calcination, the condensation with BF(4)(-) as the promoter progresses to a large extent to furnish a [Si(OSi-)(4)]/([HOSi(OSi-)(3)] + [(HO)(2)Si(OSi-)(2)]) ratio of 6.2, which is greater than that of mesoporous silica formed without BF(4)(-) before (1.5) and even after calcination (3.5) to promote thermal condensation in the solid state.

A specially designed experimental setup including a newly constructed KBr cell, a light source, a monochromator and an IR detection system suitable for strictly calibrated IR absorption measurements was constructed in order to elucidate strange phenomenon associated with cis-trans photo-isomerization at 6.26 µm of the azobenzene core located at the center of an aryl-ether dendrimer (L5AZO). The setup used an ordinary Nichrome source to measure the photon flux, irradiation area, and photon absorption rate as exactly as possible. The photon absorption rate was obtained as 1.2×10-3 photons/s·molecule and the absorption cross section of L5AZO molecules was estimated to be 3.1×10-19 cm2/molecule. Since these values of the absorption rate and absorption cross section are not abnormal, the occurrence of a simultaneous five-photon absorption is almost impossible. Therefore, the five-photon absorption and photo-isomerization shown by L5AZO suggested that the multiphoton process was not simultaneous absorption, but possibly a sequential absorption and energy storage until the equivalent energy of isomerization was reached.

The copolymerization of oxetane with glutaric anhydride was found to proceed with bulky titanium bisphenolate (1) as the initiator. The 1H NMR spectrum of the produced copolymer shows that the copolymer contains both alternating units and oxytrimethylene units in the polymer main chain. 1 was also effective for the copolymerization of oxetane with other cyclic acid anhydrides, affording the corresponding copolymers. With the titanium bisalkolate complex (4), a copolymer rich in alternating sequences was obtained.

Upon changing the oxidation state, a reversible open-close motion of chiral molecular scissors, composed of a redox-active ferrocene pivot and an isomerizable azobenzene strap, can be realized only by UV light.

Large-area homeotropic columnar ordering of π-conjugated discotic liquid crystals (LCs) is crucial for certain device applications but generally hard to achieve. Here we report polymeric o-phenylene octamer poly-1 and its monomer 1 as the first surface modifiers for homeotropic columnar order of a variety of discotic LCs up to a macroscopic length scale. Their octameric o-phenylene parts are known to fold helically into a cylinder that is reminiscent of a π-stacked column of discotic LCs. Through-view X-ray diffraction patterns of 1 suggested that this molecule adheres to the glass substrate and directs its cylindrical axis perpendicular to the glass surface. This “face-on” orientation likely nucleates the homeotropic columnar order of discotic LC materials.

An amphiphilic hexa- peri -hexabenzocoronene self-assembles to form a π-electronic, discrete nanotubular object. The object is characterized by an aspect ratio greater than 1000 and has a uniform, 14-nanometer-wide, open-ended hollow space, which is an order of magnitude larger than those of carbon nanotubes. The wall is 3 nanometers thick and consists of helical arrays of the π-stacked graphene molecule, whose exterior and interior surfaces are covered by hydrophilic triethylene glycol chains. The graphitic nanotube is redox active, and a single piece of the nanotube across 180-nanometer-gap electrodes shows, upon oxidation, an electrical conductivity of 2.5 megohms at 285 kelvin. This family of molecularly engineered graphite with a one-dimensional tubular shape and a chemically accessible surface constitutes an important step toward molecular electronics.

When mixed with imidazolium ion-based room-temperature ionic liquid, pristine single-walled carbon nanotubes formed gels after being ground. The heavily entangled nanotube bundles were found to untangle within the gel to form much finer bundles. Phase transition and rheological properties suggest that the gels are formed by physical cross-linking of the nanotube bundles, mediated by local molecular ordering of the ionic liquids rather than by entanglement of the nanotubes. The gels were thermally stable and did not shrivel, even under reduced pressure resulting from the nonvolatility of the ionic liquids, but they would readily undergo a gel-to-solid transition on absorbent materials. The use of a polymerizable ionic liquid as the gelling medium allows for the fabrication of a highly electroconductive polymer/nanotube composite material, which showed a substantial enhancement in dynamic hardness.