Nozomi Saito

Hetero-Double-Helix Formation by an Ethynylhelicene Oligomer Possessing Perfluorooctyl Side Chains

Monomeric to pentameric (P)-ethynylhelicene oligomers possessing perfluorooctyl side chains were synthesized. The circular dichroism (CD) and vapor pressure osomometry (VPO) studies indicated the formation of a helix-dimer for the (P)-pentamer, for example, in trifluoromethylbenzene at 5 degrees C at concentrations above 2 x 10(-6) M. Compared with a (P)-pentamer possessing decyloxycarbonyl side chains, the perfluorooctyl (P)-pentamer exhibited lower solubilities in organic solvents, formed a thermodynamically more stable helix-dimer, and exhibited a mirror image CD spectrum. The perfluorooctyl (P)-pentamer formed a hetero-helix dimer with a decyloxycarbonyl (M)-pentamer but not with a (P)-pentamer. It indicated higher stability of the hetero-helix dimer over the homo-helix dimers.

Two‐Component Fibers/Gels and Vesicles Formed from Hetero‐Double‐Helices of Pseudoenantiomeric Ethynylhelicene Oligomers with Branched Side Chains

A methodology for the formation of fibers/gels and vesicles by molecular assembly and for controlling their properties is presented. Two-component systems of pentamer (P)-5 and tetramer (M)-4 pseudoenantiomeric ethynylhelicenes with decyloxycarbonyl (D) and 4-methyl-2-(2-methylpropyl)-1-pentyloxycarbonyl (bD) side-chains have been examined. Distinct aggregates were formed by changing the solvent for the three combinations of (P)-bD-5/(M)-bD-4, (P)-D-5/(M)-bD-4, and (P)-D-5/(M)-D-4. In toluene, (P)-bD-5/(M)-bD-4, (P)-D-5/(M)-bD-4, and (P)-D-5/(M)-D-4 all formed gels and fibrous assemblies were observed by AFM. The minimum gel-forming concentration (MGC) decreased in the order (P)-bD-5/(M)-bD-4>(P)-D-5/(M)-bD-4>(P)-D-5/(M)-D-4. In diethyl ether, vesicular formation was observed by dynamic light scattering (DLS), AFM, and TEM, and the size of the vesicles decreased in the order (P)-bD-5/(M)-bD-4>(P)-D-5/(M)-bD-4>(P)-D-5/(M)-D-4. Both fiber/gel and vesicle formation were accompanied by enhanced CDs and redshifted UV/Vis absorption bands with a change in color to deep yellow. These are novel two-component oligomeric systems that form assemblies of fibers/gels or vesicles depending on the solvent, and the structures and properties of the assemblies can be fine-tuned by changing the combination of oligomers. In m-difluorobenzene, a homogeneous solution was obtained with (P)-D-5/(M)-bD-4, which again exhibits enhanced CDs and redshifted UV/Vis absorptions. Vapor pressure osmometry analysis showed the formation of a bimolecular heteroaggregate. The study has indicated that pseudoenantiomeric oligomers form hetero-double-helices that hierarchically assemble to form fibers/gels and vesicles.

Synthesis, Double-Helix Formation, and Higher-Assembly Formation of Chiral Polycyclic Aromatic Compounds: Conceptual Development of Polyketide Aldol Synthesis

Polycyclic aromatic compounds are an important group of substances in chemistry, and the study of their properties is a subject of interest in the development of drugs and materials. We have been conducting studies to develop chiral polycyclic aromatic compounds, i.e., helicenes and equatorenes. These helical molecules showed notable aggregate-forming properties and the capability for chiral recognition exerted by noncovalent bond interactions, which were not observed in compounds with central chirality. Homo- and hetero-double-helix-forming helicene oligomers were developed, and the latter self-assembled to form gels and vesicles. In this article, we describe such hierarchical studies of polycyclic aromatic compounds, which were started from polyketide aldol synthesis.

Two types of two-component gels formed from pseudoenantiomeric ethynylhelicene oligomers.

Two-component gels formed from pseudoenantiomeric ethynylhelicene oligomers in toluene exhibited two different properties depending on difference in numbers of helicenes in the two components. The combinations (M)-5/(P)-4, (M)-6/(P)-4, and (M)-7/(P)-4, which contained oligomers with comparable numbers of helicenes, formed transparent gels (Type I gels). The combinations (M)-6/(P)-3, (M)-7/(P)-3, and (M)-8/(P)-3, which contained oligomers with considerably different numbers of helicenes, formed turbid gels (Type II gels). Negative Cotton effects were observed for the Type I gels in the region between 350 and 450 nm, and were positive for the Type II gels, despite the use of (M)-oligomers for the longer components. UV/vis exhibited absorption maxima at 350 nm for the Type I gels and at 338 nm for the Type II gels. Different behaviors in gel formation processes were observed by fluorescence studies. Atomic force microscopy analysis showed fiber structures of 25-50 nm diameter for Type I gels and bundles of 100-150 nm diameter for Type II gels. The stoichiometry in gel formation also differed: The Type I gels showed 1:1 stoichiometry of the two components; the Type II gels showed no 1:1 stoichiometry, likely 1:2 stoichiometry. Using the Type I and II gels, two-layer gel systems were constructed.

Fluorescent Gold Nanoparticles: Synthesis of Composite Materials of Two‐Component Disulfide Gels and Gold Nanoparticles

Pseudoenantiomeric ethynylhelicene oligomers containing a disulfide group formed two-component gels, which showed different solvent properties from gels without the disulfide group. The disulfide gels reacted with gold nanoparticles, and the resulting organic-inorganic composite materials exhibited fluorescence emission between 600-800 nm, along with emission from the oligomers at 450 nm. The disulfide gels and isolated gold nanoparticles loaded with the oligomers did not show the former emission. The 600-800 nm emission reversibly disappeared upon sol formation with heating, which was accompanied by an enhancement of the emission at 450 nm. The novel emission was also observed in the solid state.

Synthesis, π‐Face‐Selective Aggregation, and π‐Face Chiral Recognition of Configurationally Stable C3‐Symmetric Propeller‐Chiral Molecules with a π‐Core

The C3 -symmetric propeller-chiral compounds (P,P,P)-1 and (M,M,M)-1 with planar π-cores perpendicular to the C3 -axis were synthesized in optically pure states. (P,P,P)-1 possesses two distinguishable propeller-chiral π-faces with rims of different heights named the (P/L)-face and (P/H)-face. Each face is configurationally stable because of the rigid structure of the helicenes contained in the π-core. (P,P,P)-1 formed dimeric aggregates in organic solutions as indicated by the results of (1) H NMR, CD, and UV/Vis spectroscopy and vapor pressure osmometry analyses. The (P/L)/(P/L) interactions were observed in the solid state by single-crystal X-ray analysis, and they were also predominant over the (P/H)/(P/H) and (P/L)/(P/H) interactions in solution, as indicated by the results of (1) H and 2D NMR spectroscopy analyses. The dimerization constant was obtained for a racemic mixture, which showed that the heterochiral (P,P,P)-1/(M,M,M)-1 interactions were much weaker than the homochiral (P,P,P)-1/(P,P,P)-1 interactions. The results indicated that the propeller-chiral (P/L)-face interacts with the (P/L)-face more strongly than with the (P/H)-face, (M/L)-face, and (M/H)-face. The study showed the π-face-selective aggregation and π-face chiral recognition of the configurationally stable propeller-chiral molecules.

Deterministic and Stochastic Chiral Symmetry Breaking Exhibited by Racemic Aminomethylenehelicene Oligomers

Racemic mixtures of aminomethylenehelicene (P)- and (M)-pentamers exhibited deterministic and stochastic chiral symmetry breaking during hetero-double-helix formation and self-assembly in solution. Heating a 50:50 mixture of (P)- and (M)-pentamers at 90 °C, and then cooling the mixture to 70 °C resulted in hetero-double-helix formation; a Cotton effect with negative Δε at λ=315 nm appeared. Chiral self-assembly occurred when the mixture was cooled to 25 °C. A strong tendency of deterministic chiral symmetry breaking appeared at the molecular and self-assembled levels, which was indicated by the negative Δε at λ=315 nm that appeared in most cases in repeated experiments. Mixtures containing 60:40 and 40:60 (P)-/(M)-pentamers also self-assembled with the same chirality. When a homo-double-helix (P)-/(M)-pentamer and a random coil (M)-/(P)-pentamer were mixed, the chiral self-assembly formed stochastically, and heating and cooling resulted in deterministic chiral symmetry breaking.

Spatially Heterogeneous Nature of Self-Catalytic Reaction in Hetero-Double Helix Formation of Helicene Oligomers.

A 1:1 mixture of pseudoenantiomeric aminomethylenehelicene oligomers, (P)-tetramer and (M)-pentamer, in fluorobenzene show a self-catalytic phenomenon in the formation of hetero-double helices from random coils. This study visualizes the spatially heterogeneous nature of the self-catalytic reaction in dilute solution. UV/Vis imaging analysis of the mixture at 70 °C, containing random coils, exhibits a homogeneous bright area. When the solution is cooled from 70 to 30 °C and held at that temperature, dark domains of approximately 1 mm in size appear, which move approximately at a rate of 1 mm min-1 . The dark domains indicate that weaker UV/Vis absorption results from the formation of hetero-double helices, which is supported by circular dichroism (CD) imaging experiments. Then a homogeneous mixture is regenerated upon heating to 55 °C, as shown by CD imaging. Under self-catalytic conditions, a homogeneous solution spontaneously changed to a heterogeneous solution in the process of hetero-double-helix formation.

Homo-Double-Helix Formation of Ethynylhelicene Oligomers Possessing Various Side Chains

The effects of side chains on homo-double helix formation of ethynylhelicene oligomers were systematically studied. It was shown that side chains have notable effects on the thermodynamic stability of homo-double helices in organic media. This observation can be explained by the arrangement of soft/hard moieties: A regular alternating arrangement of soft/hard and electron-rich/deficient moieties can form a rigid aggregate, which results in stable homo-double helix formation. The result shows that changing side chains can be an efficient method of obtaining diverse double helices.

Higher-Assembly Formation of Pseudoenantiomeric Ethynylhelicene Oligomers

The development of molecular assembled systems of fibers and vesicles using synthetic molecules is an interesting subject, which can lead to the creation of novel functional materials. This chapter describes a methodology of forming diverse two-component assemblies of fibers and vesicles employing pseudoenantiomeric ethynylhelicene oligomers. The assembly formation was controlled by changing the solvent, and fibrous assemblies and vesicles were formed in toluene and diethyl ether, respectively. It was also shown that both assemblies were formed from hetero-double helices by lateral intercomplex interactions. The results remind us of the assembly formation of biological proteins, with regard to the fact that small molecules are hierarchically bottom-upped to larger assemblies by synergism of weak interactions. It should also be noted that the structures and properties of these assemblies were fine-tuned by changing the combination of compounds.