Umbrella-Shaped Amphiphiles: Internal Alkylation of an Aromatic Micelle and Its Impact on Cavity Features.

To develop new hybrid micelles with alkyl/polyaromatic core-shell structures, we synthesized umbrella-shaped amphiphiles bearing a bent anthracene dimer with a linear alkyl chain (i.e., octyl and hexadecyl groups). The amphiphiles quantitatively assemble into spherical micelles (~2-3 nm in core diameter), possessing an alkylated cavity surrounded by a polyaromatic framework, in water. The alkylation significantly enhances the stability of the micellar structures against dilution (up to 9 µM) and heat (up to >120 °C). The highly condensed hexadecyl core of the hybrid micelle, as indicated by solvatochromic guest probes, displays increased uptake ability toward large alkylated metallodyes. Interestingly, efficient uptake of aromatic macrocycles (i.e., [n]cycloparaphenylenes) by the present micelle provides pseudorotaxane-shaped host-guest composites with high emissivity (ΦF=up to 35 %). Internal multi-alkylation of an aromatic micelle can thus successfully enhance its assembly stability/guest uptake functions.

Facile access to pyridinium-based bent aromatic amphiphiles: nonionic surface modification of nanocarbons in water.

Efficient water-solubilization of nanocarbons is desirable for both their biological and material applications, but so far has mainly relied on covalent modifications or amphiphiles featuring ionic side-chains. Here, we report a facile 2-4-step synthesis of pyridinium-based, bent aromatic amphiphiles with modular nonionic side-chains (i.e., CH3 and CH2CH2(OCH2CH2)2-Y (Y = OCH3, OH, and imidazole)). The new amphiphiles quantitatively self-assemble into ≈2 nm-sized aromatic micelles in water independent of the side-chain. Importantly, efficient water-solubilization and nonionic surface modification of various nanocarbons (e.g., fullerene C60, carbon nanotubes, and graphene nanoplatelets) are achieved through noncovalent encircling with the bent amphiphiles. The resultant imidazole-modified nanocarbons display a pH-responsive surface charge, as evidenced by NMR and zeta-potential measurements. In addition, solubilization of a nitrogen-doped nanocarbon (i.e., graphitic carbon nitride) in the form of 10-30 nm-sized stacks is also demonstrated using the present amphiphiles.

Realization of Stacked-Ring Aromaticity in a Water-Soluble Micellar Capsule.

Stacked-ring aromaticity arising from the close stacking of antiaromatic π-systems has recently received considerable attention. Here, we realize stacked-ring aromaticity via a rational supramolecular approach. A nanocapsule composed of bent polyaromatic amphiphiles was employed to encapsulate several antiaromatic norcorrole Ni(II) complexes (NCs) in water. The resulting micellar capsules display high stability toward heating and concentration change. The encapsulation resulted in the appearance of a broad absorption band in the near-infrared region, which is characteristic of norcorroles with close face-to-face stacking. Importantly, a meso-isopropyl NC, which does not exhibit π-stacking even in a concentrated solution or the crystalline phase, adopted π-stacking with stacked-ring aromaticity in the supramolecular micellar capsule.

Aromatic micelles: toward a third-generation of micelles.

Micelles are useful and widely applied molecular assemblies, formed from amphiphilic molecules, in water. The majority of amphiphiles possess an alkyl chain as the hydrophobic part. Amphiphiles bearing hydrophilic and hydrophobic polymer chains generate so-called polymeric micelles in water. This review focuses on the recent progress of "aromatic micelles", formed from bent polyaromatic/aromatic amphiphiles, for the development of third-generation micelles. Thanks to multiple host-guest interactions, e.g., the hydrophobic effect and π-π/CH-π interactions, the present micelles display wide-ranging uptake abilities toward various hydrophobic compounds in water. In addition to such host functions, new stimuli-responsive aromatic micelles with pH, light, and redox switches, aromatic oligomer micelles, saccharide-coated aromatic micelles, and related cycloalkane-based micelles were recently developed by our group.

A Redox-Responsive Ferrocene-Based Capsule Displaying Unusual Encapsulation-Induced Charge-Transfer Interactions.

A ferrocene-based capsule is spontaneously and quantitatively formed in water by the assembly of bent amphiphiles carrying two ferrocene units. The disassembly and assembly of the new organometallic capsule, with a well-defined and highly condensed ferrocene core, are demonstrated by chemical redox stimuli in a fully reversible fashion under ambient conditions. In contrast to previously reported multiferrocene assemblies, only the present capsule efficiently encapsulates typical organic/inorganic dyes as well as electron-accepting molecules in water. As a result, unusual host-guest charge-transfer (CT) interactions, displaying relatively wide absorption bands in the visible to near-infrared region (λ=650-1350 nm), are observed upon the encapsulation of acceptors (i.e., chloranil and TCNQ). The resultant encapsulation-induced CT interactions can be released by a redox stimulus through the disassembly of the capsule.

Facile Processing of Unsubstituted π-Conjugated Aromatic Polymers through Water-solubilization Using Aromatic Micelles.

π-Conjugated aromatic polymers (πCAPs) are central components of functional materials yet suffer from insolubility without multiple covalent substituents on their backbones. We herein disclose a new strategy for the facile processing of unsubstituted heterocyclic πCAPs (i.e., poly(para-phenylene-2,6-benzobisoxazole) and poly(benzimidazobenzo-phenanthroline)), independent of the polymer length, via non-covalent encircling with aromatic micelles, composed of bent aromatic amphiphiles, in water. The UV/Visible studies reveal that the efficiencies of the present encircling method are ≈10 to 50-fold higher than those using conventional amphiphiles under the same conditions. The AFM and SEM analyses of the resultant aqueous polymer composites show that otherwise insoluble πCAPs form fine bundles (e.g., ≈1 nm in thickness) in the tubular aromatic micelles, through efficient π-stacking interactions. In the same way, pristine poly(para-phenylene) can be dissolved in water, displaying enhanced fluorescence (10-fold), relative to the polymer solid. Two types of unsubstituted πCAPs are likewise co-encircled in water, indicated by UV/Visible analysis. Importantly, aqueous processing of the encircled πCAPs into free-standing single- or multicomponent films with submicrometer thickness is demonstrated through a simple filtration-annealing protocol.

Selective Encapsulation and Unusual Stabilization of cis-Isomers by a Spherical Polyaromatic Cavity.

To explore new cavity functions, we herein employed cis-trans stereoisomers with a N=N, C=C, or C=N unit as guest indicators for a polyaromatic capsule. Thanks to the rigid, spherical cavity with a diameter of ∼1 nm, azobenzene and stilbene derivatives are quantitatively encapsulated by the capsule with 100 % cis-selectivity in water. The isomerization of the cis-azo compound is suppressed against heat and light in the cavity, due to the confinement effect. Furthermore, C,N-diphenyl imine derivatives are quantitatively encapsulated by the capsule in water and adopt an otherwise unstable cis-form. The polyaromatic cavity suppresses the hydrolysis of the imines in water, even at elevated temperature, due to the shielding effect. Accordingly, the properties of the cis-trans isomers could be largely altered through supramolecular manipulation.

CH-π Multi-Interaction-Driven Recognition and Isolation of Planar Compounds in a Spheroidal Polyaromatic Cavity.

π-π Interactions are established as a powerful supramolecular tool, whereas the usability of CH-π interactions has been rather limited so far. Here we present (i) selective binding of planar polyaromatics and (ii) effective isolation of planar metal complexes by a polyaromatic capsule, utilizing multiple CH-π interactions. In the spheroidal cavity, one molecule of large and medium-sized polyaromatic molecules (i. e., coronene and pyrene) is exclusively bound from mixtures bearing the same number of aromatic CH groups. Theoretical studies reveal that multiple host-guest CH-π interactions (up to 32 interactions) are the predominant driving force for the observed selectivity. In addition, one molecule of planar metal complexes (i. e., porphine and bis(acetylacetonato) Cu(II) complexes) is quantitatively bound by the capsule through aromatic and aliphatic CH-π multi-interactions, respectively. The ESR and theoretical studies demonstrate the isolation capability of the capsular framework and an unusual polar environment in the polyaromatic cavity.

A Porous Polyaromatic Solid for Vapor Adsorption of Xylene with High Efficiency, Selectivity, and Reusability.

Development of porous materials capable of capturing volatile organic compounds (VOCs), such as benzene and its derivatives, with high efficiency, selectivity, and reusability is highly demanded. Here we report unusual vapor adsorption behavior toward VOCs by a new porous solid, composed of a polyaromatic capsule bearing a spherical nanocavity with subnano-sized windows. Without prior crystallization and high-temperature vacuum drying, the porous polyaromatic solid exhibits the following five features: vapor adsorption of benzene over cyclohexane with 90 % selectivity, high affinity toward o-xylene over benzene and toluene with >80 % selectivity, ortho-selective adsorption ability (>50 %) from mixed xylene isomers, tight VOCs storage even under high temperature and vacuum conditions, and at least 5 times reusability for xylene adsorption. The observed adsorption abilities are accomplished at ambient temperature and pressure within 1 h, which has not been demonstrated by organic/inorganic porous materials reported previously.

An Adamantane Capsule and its Efficient Uptake of Spherical Guests up to 3 nm in Water.

Efficient uptake of small to large guests, with a large difference in relative size, is quite rare for synthetic host compounds. Herein we designed and prepared a micellar capsule, composed of bent amphiphiles bearing two adamantyl groups, as a new host with a well-defined nanostructure. Unlike previous covalent, coordination, and hydrogen-bonding hosts, the adamantane-based capsule displays unusual uptake abilities toward spherical molecules with small (∼0.6 nm in diameter; e.g., adamantane) to medium size (∼1 nm; e.g., fullerene) as well as large size (∼3 nm; i.e., metal-organic polyhedra (MOP)), where the size differences are up to 5-fold, in water. Moreover, the resultant MOP-uptaking capsule incorporates medium-sized molecules (e.g., perylene and eosin Y) into the polyhedral cavity to generate ternary core-shell structures.

Supramolecular Singlet Fission of Pentacene Dimers within Polyaromatic Capsules.

We herein report a new set of supramolecular nanotools for the generation and modulation of singlet fission (SF) of noncovalent/covalent pentacene dimers. Two molecules of a pentacene monomer with bulky substituents are facilely encapsulated by a polyaromatic capsule, composed of naphthalene-based bent amphiphiles, in water. The encapsulated noncovalent dimer converts to otherwise undetectable triplet pairs and an individual triplet in high quantum yields (179% and 53%, respectively) even under high dilution conditions. Within the capsule, a covalently linked pentacene dimer with bulky groups generates two triplet pair intermediates in parallel, which are hardly distinguished in bulk solution, in excellent total quantum yield (196%). The yield of the individual triplet is enhanced by 1.6 times upon encapsulation. For both types of pentacene dimers, the SF features can be readily tuned by changing the polyaromatic panels of the capsule (i.e., anthracene and phenanthrene).

An Aromatic Oligomer Micelle: Large Enthalpic Stabilization and Selective Oligothiophene Uptake.

An aromatic oligomer micelle, featuring both high stability and high uptake ability, was quantitatively formed in water from amphiphilic oligomers, composed of three bent polyaromatic amphiphiles connected alternately by two hydrophilic chains. The well-defined micelle, with a diameter of ca. 2 nm, remains intact even under highly diluted conditions (ca. 3 µM) and at elevated temperature (>130 °C), due to the polyaromatic chelate effect. The thermodynamic studies reveal that large enthalpic gain (ΔH=-110 kJ mol-1 ) is the key for the micelle formation. The oligomer micelle selectively encapsulates unsubstituted oligothiophenes (≥4-mer) to a high degree and the resultant, aqueous host-guest complexes display unusual emission derived from the multiply stacked oligomers. Furthermore, facile uptake and release of unsubstituted polythiophenes can be achieved using the oligomer micelle.

An Aromatic Micelle-Based Saccharide Cluster with Changeable Fluorescent Color and its Protein Interactions.

To develop a new type of synthetic saccharide clusters with changeable fluorescent colors, we herein designed a multisaccharide-coated aromatic micelle. The new cluster forms in water through the quantitative assembly of bent polyaromatic amphiphiles bearing three mannose groups. The spherical assembly, with a 2 nm-sized polyaromatic core and ca. 18 saccharide pendants, is stable even under high dilution conditions (up to 0.02 mM). The emission intensity and color of the saccharide cluster can be altered from moderate blue (ΦF =19 %) to strong red, orange, and green (ΦF up to 67 %) upon encapsulation of hydrophobic fluorescent dyes in water. Moreover, the present fluorescent clusters, both with and without the dyes, display selective interactions with mannose-binding proteins in vitro.

Preparation of a Multicarbazole-Based Nanocapsule Capable of Largely Modulating Guest Spectroscopic Properties in Water.

A nanocapsule composed of multiple carbazole panels (ca. 12 panels) was quantitatively generated from bent carbazole-based amphiphiles in water. Unlike previously reported macrocycles and coordination cages bearing several carbazole panels, the resultant nanocapsule displays enhanced emissivity and improved electrochemical stability as compared with the monomeric amphiphile. The spectroscopic properties of substituted coumarin and boron-dipyrromethene dyes can be modulated upon encapsulation by the nanocapsule in water. In the cavity, a highly blue-shifted absorption band is observed from largely twisted coumarin dyes and two absorption bands are found from boron-dipyrromethene dimers stacked in an unusual L-shaped fashion. Moreover, the encapsulated dimers exhibit unique excimer-like emission.

Synthesis of Azaylide-Based Amphiphiles by the Staudinger Reaction.

Catalyst- and reagent-free reactions are powerful tools creating various functional molecules and materials. However, such chemical bonds are usually hydrolysable or require specific functional groups, which limits their use in aqueous media. Herein, we report the development of new amphiphiles through the Staudinger reaction. Simple mixing of chlorinated aryl azide with a hydrophilic moiety and various triarylphosphines (PAr3) gave rise to azaylide-based amphiphiles NPAr3, rapidly and quantitatively. The obtained NPAr3 formed ca. 2 nm-sized spherical aggregates (NPAr3)n in water. The hydrolysis of NPAr3 was significantly suppressed as compared with those of non-chlorinated amphiphiles nNPAr3. Computational studies revealed that the stability is mainly governed by the decrease in LUMO around the phosphorus atom owing to the o-substituted halogen groups. Furthermore, hydrophobic dyes such as Nile red and BODIPY were encapsulated by the spherical aggregates (NPAr3)n in water.

Anisotropic Contraction of a Polyaromatic Capsule and Its Cavity-Induced Compression Effect.

Anisotropic contraction of a spherical polyaromatic capsule was demonstrated through simple meta-to-ortho modification of the bent polyaromatic ligands. The resultant capsule, composed of two metal ions and four ortho-substituted ligands, possesses a spheroidal cavity (1.1 nm × 1.5 nm × 1.5 nm) fully encircled by a polyaromatic framework. One large planar or bowl-shaped molecule (e.g., porphine or sumanene) is quantitatively bound by the capsule, in which the cavity-induced compression effect causes the acceleration of the bowl-to-bowl inversion of sumanene. Temperature-dependent 1H NMR analysis revealed that the activation energy of the inversion decreases greatly (ΔG⧧ = -2.8 kcal mol-1 at 318 K) upon encapsulation, whereas the opposite effect was observed in the spherical cavity of the previous polyaromatic capsule.

Synthesis of a Black Dye with Absorption Capabilities Across the Visible-to-Near-Infrared Region: A MO-Mixing Approach via Heterometal Coordination of Expanded Porphyrinoid.

An expanded metalloporphyrin-based "black dye" Au-Pd oxohexaphyrin (AuPd-1) with absorption capabilities across the visible-to-near-infrared (NIR) range was synthesized. This black dye, AuPd-1, possessed efficient light-harvesting and photostable capabilities, which were indicative of superior photothermal (PT) conversion abilities. Encapsulation of AuPd-1 with a micellar nanocapsule resulted in a compound that demonstrated intense photoacoustic (PA) properties in the NIR region in water. This finding indicated how metal (d)-ligand (π) molecular orbital interactions in metalloporphyrins could aid in the design of visible-to-NIR light-harvesting black dyes for PT and PA applications.

Bent Anthracene Dimers as Versatile Building Blocks for Supramolecular Capsules.

This Account provides a comprehensive summary of our 1-decade-long investigations into bent anthracene dimers as versatile building blocks for supramolecular capsules. The investigations initiated in 2008 with the design of an anthracene dimer with a meta-phenylene spacer bearing two substituents on the convex side. Using the bent polyaromatic building block, we began to develop novel supramolecular capsules from two different synthetic approaches. One is a coordination approach, which was pursued by converting the building block into a bent ligand with two pyridine units at the terminal positions. The ligands quantitatively assemble into an M2L4-type capsule through coordination bonding with metal ions. The other is a π-stacking approach, which was followed by utilizing the block as a bent amphiphilic molecule with two trimethylammonium groups at the spacer. In water, the amphiphiles spontaneously assemble into a micelle-type capsule through the hydrophobic effect and π-stacking interactions. Simple modification of the building block allowed us to prepare a wide variety of coordination capsules as well as π-stacking capsules, bearing different hydrophilic side-chains, terminal substitutions, connecting units, polyaromatic panels, or spacer units. The coordination capsule possesses a rigid cavity, with a diameter of ∼1 nm, surrounded by multiple anthracene panels. The spherical polyaromatic cavity binds various synthetic molecules (e.g., paracyclophanes, corannulene, BODIPY, and fullerene C60) in aqueous solutions. With the aid of the polyaromatic shell, photochemically and thermally reactive radical initiators and oligosulfurs are greatly stabilized in the cavity. Biomolecules such as hydrophilic sucrose and oligo(lactic acid)s as well as hydrophobic androgenic hormones are bound by the capsule with high selectivity. In addition, long amphiphilic poly(ethylene oxide)s are threaded into the closed shell of the capsule(s) to generate unusual pseudorotaxane-shaped host-guest complexes in water. In contrast, the π-stacking capsule furnishes a flexible cavity, adaptable to the size and shape of guest molecules, encircled by multiple anthracene panels. In water, the capsule binds hydrophobic fluorescent dyes (e.g., Nile red and DCM) in the cavity. Simple grinding of the bent amphiphile with highly hydrophobic nanocarbons such as fullerenes, nanographenes, and carbon nanotubes (followed by sonication) as well as metal-complexes such as Cu(II)-phthalocyanines and Mn(III)-tetraphenylporphyrins leads to the efficient formation of water-soluble host-guest complexes upon encapsulation. Red emission from otherwise water-deactivated Eu(III)-complexes is largely enhanced in water through encapsulation. Moreover, the incorporation of pH- and photoswitches into the amphiphile affords stimuli-responsive π-stacking capsules, capable of releasing bound guests by the addition of acid and light irradiation, respectively, in water. The host functions of the coordination and π-stacking capsules are complementary to each other, which enables selection of the capsule-type depending on the envisioned target. We are convinced that continued investigation of the present supramolecular capsules featuring the bent anthracene dimer and its derivatives will further increase their value as advanced molecular tools for synthetic, analytical, material, biological, and/or medical applications.

N-Doping of Polyaromatic Capsules: Small Cavity Modification Leads to Large Change in Host-Guest Interactions.

To gain insight into the host functions of a nanocavity encircled by both polyaromatic panels and heteroatoms, nitrogen-doped polyaromatic capsules were successfully synthesized from metal ions and pyridine-embedded, bent anthracene-based ligands. The new capsules display unique host-guest interactions in the isolated cavities, which are distinct from those of the undoped analogues. Besides the inclusion of Ag+ ions, the large absorption change of fullerene C60 and altered emission of a BODIPY dimer are observed upon encapsulation by the present hosts. Moreover, the N-doped capsule exhibits specific binding ability toward progesterone and methyltestosterone, known as a natural female and synthetic male hormone, respectively, in water.

Recognition and Stabilization of Unsaturated Fatty Acids by a Polyaromatic Receptor.

Selective recognition of natural fatty acids is intrinsically difficult owing to the long, flexible, and poorly interactive hydrocarbon chains. Inspired by biological recognition systems, we herein demonstrate the exclusive binding of a monounsaturated fatty acid by an artificial polyaromatic receptor from a mixture of the unsaturated and corresponding saturated substrates (i.e., oleic and stearic acids) in water. The selectivity stems from multiple CH-π/π-π interactions between the host framework and the guest in its roughly coiled conformation. Moreover, competitive binding experiments elucidate higher binding affinities of the receptor for oligo- and polyunsaturated fatty acids (e.g., α-linolenic acid and EPA). Within the receptor, the biosubstrates are remarkably stabilized against air, light, and heat owing to the polyaromatic shielding effect.