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.

Photocontrol over self-assembled nanostructures of π-π stacked dyes supported by the parallel conformer of diarylethene.

Diarylethenes (DAEs) have rarely been used in the design of photoresponsive supramolecular assemblies with a well-defined morphology transition owing to rather small structural changes upon photoisomerization. A supramolecular design based on the parallel conformation of DAEs enables the construction of photoresponsive dye assemblies that undergo remarkable nanomorphology transitions. The cooperative stacking of perylene bisimide (PBI) dyes was used to stabilize the parallel conformer of DAE through complementary hydrogen bonds. Atomic force microscopy, UV/Vis spectroscopy, and molecular modeling revealed that our DAE and PBI building blocks coassembled in nonpolar solvent to form well-defined helical nanofibers featuring J-type dimers of PBI dyes. Upon irradiating the coassembly solution with UV and visible light in turn, a reversible morphology change between nanofibers and nanoparticles was observed. This system involves the generation of a new self-assembly pathway by means of photocontrol.

Covalent modular approach for dimension-controlled self-organization of perylene bisimide dyes.

Organogels: Dimerization of perylene bisimide dyes through an oligomethylene linker enabled the facile control over columnar and lamellar self-organized architectures by an odd/even effect with respect to the number of methylene groups. The difference in the self-organized architectures was shown to have an impact on their material morphologies, as well as charge-carrier mobilities (see scheme).

Photophysical properties of substituted homoleptic and heteroleptic phenylimidazolinato Ir(III) complexes as a blue phosphorescent material.

Iridium complexes are one of the most important materials for fabrication of organic light emitting diodes (OLEDs). There are difficulties in the preparation of blue phosphorescent complexes with respect to chromaticity, emission efficiency, and stability of the material, compared with green and red phosphorescent complexes. Control of the frontier orbital energy level (HOMO-LUMO) is the sole method to achieve better blue phosphorescent iridium complexes by appropriate ligand selection and the introduction of adequate substituents. Homoleptic and heteroleptic iridium(III) tris(phenylimidazolinate) complexes were synthesized, and the effect of the substituents on their nature in the excited state was examined. Density functional theory calculation showed that the imidazolinato complexes have the HOMO localized at the iridium d- and phenyl π-orbitals. The LUMO is also localized on the phenyl moiety with a much higher population than HOMO. This LUMO is quite different from other complexes, such as iridium(III) tris(phenylpyridinate) and tris(phenylpyrazolinate) complexes. Therefore, substitution with π-electron donating groups and electron withdrawing groups induces blue and red spectral shifts, respectively, which is the reverse shift exhibited by other complexes. The ancillary ligand (acetylacetone) acts as a path for nonradiative deactivation in the blue phosphorescent complexes.

Control over hierarchy levels in the self-assembly of stackable nanotoroids.

We report a precise control over the hierarchy levels in the outstanding self-organization process shown by chiral azobenzene dimer 1. This compound forms uniform toroidal nanostructures that can hierarchically organize into chiral nanotubes under the control by temperature, concentration, or light. The nanotubes further organized into supercoiled fibrils, which finally intertwined to form double helices with one-handed helical sense.

Supramolecularly engineered perylene bisimide assemblies exhibiting thermal transition from columnar to multilamellar structures.

Perylene 3,4:9,10-tetracarboxylic acid bisimide (PBI) was functionalized with ditopic cyanuric acid to organize it into complex columnar architectures through the formation of hydrogen-bonded supermacrocycles (rosette) by complexing with ditopic melamines possessing solubilizing alkoxyphenyl substituents. The aggregation study in solution using UV-vis and NMR spectroscopies showed the formation of extended aggregates through hydrogen-bonding and π-π stacking interactions. The cylindrical fibrillar nanostructures were visualized by microscopic techniques (AFM, TEM), and the formation of lyotropic mesophase was confirmed by polarized optical microscopy and SEM. X-ray diffraction study revealed that a well-defined hexagonal columnar (Col(h)) structure was formed by solution-casting of fibrillar assemblies. All of these results are consistent with the formation of hydrogen-bonded PBI rosettes that spontaneously organize into the Col(h) structure. Upon heating the Col(h) structure in the bulk state, a structural transition to a highly ordered lamellar (Lam) structure was observed by variable-temperature X-ray diffraction, differential scanning calorimetry, and AFM studies. IR study showed that the rearrangement of the hydrogen-bonding motifs occurs during the structural transition. These results suggest that such a striking structural transition is aided by the reorganization in the lowest level of self-organization, i.e., the rearrangement of hydrogen-bonded motifs from rosette to linear tape. A remarkable increase in the transient photoconductivity was observed by the flash-photolysis time-resolved microwave conductivity (FP-TRMC) measurements upon converting the Col(h) structure to the Lam structure. Transient absorption spectroscopy revealed that electron transfer from electron-donating alkoxyphenyl groups of melamine components to electron-deficient PBI moieties takes place, resulting in a higher probability of charge carrier generation in the Lam structure compared to the Col(h) structure.

Photoreversible supramolecular polymerisation and hierarchical organization of hydrogen-bonded supramolecular co-polymers composed of diarylethenes and oligothiophenes.

Diarylethene 1 equipped with two monotopic melamine hydrogen-bonding sites and oligothiophene-functionalized ditopic cyanurate (OTCA) were mixed in a nonpolar solvent to form AA-BB-type supramolecular co-polymers (SCPs) bearing photoswitchable moieties in their main chains and extended π systems as side chains. UV/Vis, fluorescence, dynamic light scattering (DLS), TEM, and AFM studies revealed that the two functional co-monomers formed flexible quasi-one-dimensional SCPs in solution that hierarchically self-organized into helical nanofibers through H-aggregation of the oligothiophene side chains. Upon irradiating the SCPs with UV light, a transition occurred from the H-aggregated state to non-aggregated monomeric oligothiophene side chains, as shown by spectroscopic studies, which indicates the formation of small oligomeric species held together only by hydrogen-bonding interactions. TEM and AFM visualized unfolded fibrils corresponding to elongated single SCP chains formed upon removal of solvent. The helical nanofibers were regenerated upon irradiating the UV-irradiated solution with visible light. These results demonstrated that the supramolecular polymerisation followed by hierarchical organization can be effectively controlled by proper supramolecular designs using diarylethenes and π-conjugated oligomers.

Rational construction of perylene bisimide columnar superstructures with a biased helical sense.

Discotic supramolecular complexes bearing six perylene bisimide (PBI) chromophores were prepared by mixing monotopically triple-hydrogen-bonding melamines equipped with two PBI chromophores and two 3,7-dimethyloctyl chiral handles with tritopically triple-hydrogen-bonding cyanuric acid (CA). UV/Vis and fluorescence titration experiments demonstrated that the discotic complexes were formed in methylcyclohexane by the 3:1 complexation between the melamines and CA. TEM and AFM studies revealed that the complexes hierarchically organize into fibrous columnar assemblies, which eventually results in the formation of organogels. Circular dichroism (CD) and flash-photolysis time resolved microwave conductivity measurements revealed the presence of extended chiral stacks of PBI chromophores within the columns. The anisotropy factors of the columnar assemblies are remarkably high (g=1.5×10(-3)) when considering the presence of only one 3,7-dimethyloctyl chiral handle per perylene chromophore, suggesting that the columnar structures have a biased helical sense. The fact that the chiral centers are located inside the discotic complexes rather than at their peripheries might be unique structural property responsible for the rather strong optical activities for the assemblies of this chromophore. The effective transcription of the molecular chirality to the extended columnar assemblies through the formation of unique discotic complexes enables the expression of "majority-rules" chiral amplification effect, which is unprecedented for the supramolecular assemblies of PBIs.

Structural and electronic properties of extremely long perylene bisimide nanofibers formed through a stoichiometrically mismatched, hydrogen-bonded complexation.

Extremely long nanofibers, whose lengths reach the millimeter regime, are generated via co-aggregation of a melamine-appended perylene bisimide semiconductor and a substituted cyanurate, both of which are ditopic triple-hydrogen-bonding building blocks; they co-aggregate in an unexpected stoichiometrically mismatched 1:2 ratio. Various microscopic and X-ray diffraction studies suggest that hydrogen-bonded polymeric chains are formed along the long axis of the nanofibers by the 1:2 complexation of the two components, which further stack along the short axis of the nanofibers. The photocarrier generation mechanism in the nanofibers is investigated by time-of-flight (TOF) experiments under electric and magnetic fields, revealing the birth and efficient recombination of singlet geminate electron-hole pairs. Flash-photolysis time-resolved microwave conductivity (FP-TRMC) measurements revealed intrinsic 1D electron mobilities up to 0.6 cm(2) V(-1) s(-1) within nanofibers.

Rational design of nanofibers and nanorings through complementary hydrogen-bonding interactions of functional pi systems.

A simple protocol to create nanofibers and -rings through a rational self-assembly approach is described. Whereas the melamine-oligo(p-phenylenevinylene) conjugate 1a self-aggregates to form ill-defined nanostructures, conjugate 1b, which possesses an amide group as an additional interactive site, self-aggregates to form 1D nanofibers that induce gelation of the solvent. AFM and XRD studies have shown that dimerization through the melamine-melamine hydrogen-bonding interaction occurs only for 1b. Upon complexation with 1/3 equivalents of cyanuric acid (CA), conjugate 1a provides well-defined, ring-shaped nanostructures at micromolar concentrations, which open to form fibrous assemblies at submillimolar concentrations and organogels in the millimolar concentration range. Apparently, the enhanced aggregation ability of 1a by CA is a consequence of columnar organization of the resulting discotic complex 1a(3).CA. In contrast, coaggregation of 1b with CA does not provide well-defined nanostructures, probably due to the interference of complementary hydrogen-bonding interactions by the amide group.

Two-dimensional organization of mono- and bisurea supramolecular polymers studied by scanning tunneling microscopy.

Scanning tunneling microscopy (STM) of mono- and bisurea-functionalized oligo(p-phenylenevinylene)s at solid/liquid interface visualized two-dimensionally-ordered double columnar structures of pi-conjugated segments scaffolded by one-dimensional supramolecular polymerization of urea hydrogen-bonding units. In contrast to a persistent alignment of the bisurea compound supported by twofold intermolecular urea-urea hydrogen-bonding, the building blocks in the monourea double columns shows dynamic fluctuation and defects because of their rotational motion around urea-urea hydrogen-bonding axis and/or adsorption-desorption of the individual molecules from the surface. Self-assembled structures of mono- and bisurea compounds at solid/liquid interface revealed by STM can be related to their gelation abilities in organic solvents.

Reversible transformation between rings and coils in a dynamic hydrogen-bonded self-assembly.

Several proteins, such as tobacco mosaic virus coat protein and the beta protein of the bacteriophage lambda, are known to exhibit unique dynamic self-organization processes involving ring-shaped and extended helical nanostructures triggered by chemical stimuli. However, transformation of rings into coils as observed in biological assemblies has never been realized with synthetic molecular building blocks. Oligo(p-phenylenevinylene) functionalized on one end with barbituric acid and on the other end with aliphatic tails self-organizes in aliphatic solvents to form nanorings through hydrogen-bonding and pi-stacking interactions. Upon an increase in concentration, the nanorings transform into rodlike nanostructures, which are considered to be formed through helically coiled objects consisting of quasi-one-dimensional fibers.

Unconventional hydrogen-bond-directed hierarchical co-assembly between perylene bisimide and azobenzene-functionalized melamine.

Co-assembly of ditopic perylene bisimide and azobenzene-functionalized melamine occurs with an unconventional stoichiometric ratio, providing well-defined nanostructures with a helically-coiled architecture where perylene chromophores are packed in desirable J-type arrangements.

Cyanurate-guided self-assembly of a melamine-capped oligo(p-phenylenevinylene).

An oligo(p-phenylenevinylene) capped on one end by a monotopic DAD-type triple hydrogen-bonding module shows distinct optical properties as well as self-organization behavior upon complexation with cyanurates with different numbers of ADA-type triple hydrogen-bonding sites.

Supramolecular nanoribbons and nanoropes generated from hydrogen-bonded supramolecular polymers containing perylene bisimide chromophores.

A perylene bisimide anchored with melamine hydrogen-bonding units has been prepared, and its supramolecular polymerization upon binding with N-dodecylcyanurate (CA) was examined. The resulting flexible supramolecular polymers self-organized via a pi-pi stacking interaction between perylene chromophores, affording ribbonlike aggregates in cyclic alkanes and ropelike aggregates in acyclic alkanes to form gels. [structure: see text]

Tunable interchromophore electronic interaction of a merocyanine dye in hydrogen-bonded supramolecular assemblies scaffolded by bismelamine receptors.

The absorption and fluorescence properties of a barbiturate-type donor-pi-acceptor (D-pi-A) merocyanine dye are controlled by complexation with dimeric melamine receptors featuring different tether lengths.