Exciplex Formation by Complexation of an Electron-Accepting Guest in an Electron-Donating Pillar[5]arene Host Liquid.

We present a novel system, a liquid-state pillar[5]arene decorated with tri(ethylene oxide) chains, that brings electron-donor and electron-acceptor molecules into proximity for efficient exciplex formation. The electron-accepting guests exhibit a blue-purple emission from a localized excited state upon excitation in common solvents. However, directly dissolving the guests in the electron-donating pillar[5]arene liquid (a bulk system) results in visible green emission from the formed exciplexes. In the bulk system, the guest molecules are always surrounded by excess pillar[5]arene molecules, resulting in the formation of mainly inclusion-type exciplexes. In the bulk system, energy migration occurs between the pillar[5]arene molecules. Excitation of the pillar[5]arenes results in a more intense green exciplex emission than that observed upon direct excitation of the guests. In summary, the pillar[5]arene liquid is a novel system for achieving efficient exciplex formation and energy migration that is different from typical solvent and solid systems.

Dynamic-to-Static Planar Chirality Conversion in Pillar[5]arenes Regulated by Guest Solvents or Amplified by Crystallization.

Controlling dynamic chirality and memorizing the controlled chirality are important. Chirality memory has mainly been achieved using noncovalent interactions. However, in many cases, the memorized chirality arising from noncovalent interactions is erased by changing the conditions such as the solvent and temperature. In this study, the dynamic planar chirality of pillar[5]arenes was successfully converted into static planar chirality by introducing bulky groups through covalent bonds. Before introducing the bulky groups, pillar[5]arene with stereogenic carbon atoms at both rims existed as a pair of diastereomers, and thus showed planar chiral inversion that was dependent on the chain length of the guest solvent. The pS and pR forms, regulated by guest solvents, were both diastereomerically memorized by introducing bulky groups. Furthermore, the diastereomeric excess was amplified by crystallization of the pillar[5]arene. The subsequent introduction of bulky groups yielded pillar[5]arene with an excellent diastereomeric excess (95 % de).

Thermally Responsive Poly(ethylene oxide)-Based Polyrotaxanes Bearing Hydrogen-Bonding Pillar[5]arene Rings.

Invited for the cover of this issue are Tomoki Ogoshi and co-workers at Kyoto University, Kanazawa University and Tokyo University of Agriculture and Technology. The image depicts musical notation to represent hydrogen bond networks and poly(ethylene oxide) chains. Read the full text of the article at 10.1002/chem.202005099.

Thermally Responsive Poly(ethylene oxide)-Based Polyrotaxanes Bearing Hydrogen-Bonding Pillar[5]arene Rings*.

Poly(ethylene oxide)s (PEOs) are useful polymers with good water solubility, biological compatibility, and commercial availability. PEOs with various end groups were threaded into pillar[5]arene rings in a mixture of water and methanol to afford pseudopolyrotaxanes. Corresponding polyrotaxanes were also constructed by capping COOH-terminated pseudopolyrotaxanes with bulky amines, in which multiple hydrogen bonds involving the pillar[5]arene OH groups were critically important to prevent dethreading. The number of threaded ring components could be rationally controlled in these materials, providing a simple and versatile method to tune the mechanical and thermal properties. Specifically, a polyrotaxane with a high-molecular-weight axle became elastic upon heating above the melting point of PEOs and exhibited temperature-dependent shape memory property because of the topological confinement and crosslinked hydrogen bonds.

Guest Vapor-Induced State Change of Structural Liquid Pillar[6]arene.

State change is a key phenomenon in materials science. We report the first observation of vapor-responsive reversible structural liquid-to-solid and solid-to-structural liquid state changes. We observed that a macrocyclic compound, a pillar[6]arene derivative bearing 12 n-hexyl substituents, is a room temperature structural liquid with unique properties. Formation of a host-guest complex between the pillar[6]arene cavity and the n-hexyl substituent results in a structural liquid with nanoscale structural heterogeneities. The structural liquid solidifies when exposed to competitive cyclohexane guest vapor, whereupon cyclohexane replaces the n-hexyl substituents in the pillar[6]arene cavity and the n-hexyl substituents located outside of the cavity crystallize into distinct nanolayer assemblies. The solid reverts back to the structural liquid when the cyclohexane guest is removed through heating under reduced pressure because of rethreading of the n-hexyl substituents into the cavity. The structural liquid-to-solid and solid-to-structural liquid changes are reversible through the uptake and release of cyclohexane guest vapor.

Stimuli-Responsive Supramolecular Assemblies Constructed from Pillar[ n]arenes.

Supramolecular assemblies are constructed from at least two molecules through various noncovalent bonding modes such as hydrogen bonding, cationic-anionic electrostatic interactions, aromatic interactions, metal-ligand bonding, hydrophobic-hydrophilic interactions, and charge-transfer interactions. Owing to the dynamic and reversible nature of these noncovalent bonds, the assembly and disassembly of these molecules are dynamic and reversible. Molecules self-assemble to form the most conformationally and thermally stable structures through these noncovalent interactions. The formation of these noncovalent interactions is affected by the properties of the environment such as its polarity, temperature, and pressure; thus, the structure of the assembled compounds is determined by the environment. The sizes and shapes of the supramolecular assemblies play an important role in determining their functions. Therefore, controlling their size and shape is important. Introducing stimuli-responsive groups into supramolecular assemblies is a useful way to control their size and shape. Controlling supramolecular structures and motions with external stimuli, i.e., periodic and rotational motions on the molecular scale, structures, and molecular weights at the nano- and micrometer scales, visible shrinking/expansion, and adhesive behavior at a macroscopic scale, is very useful. Macrocyclic host molecules are useful building blocks for the construction of stimuli-responsive supramolecular assemblies because their host ability can be tuned by changing the shape and electron density of the cavity. The size-dependent hosting ability of the cavity is similar to the lock-and-key model in biological systems. Stimuli-responsive supramolecular assemblies have been developed by using macrocyclic compounds such as cyclodextrins, cucurbit[ n]urils, calix[ n]arenes, crown ethers, and related macrocycles. We successfully developed new pillar-shaped macrocyclic hosts in 2008, which were coined pillar[ n]arenes. The unique structural features of pillar[ n]arenes allowed new properties. This year, 2018, marks one decade of research into pillar[ n]arene chemistry, and in that time the properties of pillar[ n]arenes have been widely investigated by various scientists. Thanks to their efforts, the characteristic properties of pillar[ n]arenes that result from their pillar-shaped structures have been elucidated. Their host ability, the chirality of their pillar-shaped structure, and their versatile functionality are unique features of pillar[ n]arenes not seen in other well-known hosts, and these properties are very useful for the creation of new stimuli-responsive supramolecular assemblies. In this Account, we describe photo-, pH- and redox-responsive supramolecular assemblies based on pillar[ n]arenes. First, we discuss molecular-scale stimuli-responsive supramolecular assemblies, i.e., pseudorotaxanes, pseudocatenanes, and supramolecular polymers. We also highlight subnanometer- and micrometer-scale stimuli-responsive supramolecular assembles such as particles and vesicles. Finally, we discuss the macroscopic stimuli-responsive structural changes of surfaces and gels. This Account will provide useful information for researchers working on not only pillar[ n]arene chemistry but also the chemistry of other macrocyclic hosts, and it will inspire new discoveries in the field of supramolecular assemblies and systems containing macrocyclic hosts.

Host-Guest Complexation Using Pillar[5]arene Crystals: Crystal-Structure Dependent Uptake, Release, and Molecular Dynamics of an Alkane Guest.

Host-guest complexation has been mainly investigated in solution, and it is unclear how guest molecules access the assembled structures of host and dynamics of guest molecules in the crystal state. In this study, we studied the uptake, release, and molecular dynamics of n-hexane vapor in the crystal state of pillar[5]arenes bearing different substituents. Pillar[5]arene bearing 10 ethyl groups yielded a crystal structure of herringbone-type 1:1 complexes with n-hexane, whereas pillar[5]arene with 10 allyl groups formed 1:1 complexes featuring a one-dimensional (1D) channel structure. For pillar[5]arene bearing 10 benzyl groups, one molecule of n-hexane was located in the cavity of pillar[5]arene, and another n-hexane molecule was located outside of the cavity between two pillar[5]arenes. The substituent-dependent differences in molecular arrangement influenced the uptake, release, and molecular dynamics of the n-hexane guest. The substituent effects were not observed in host-guest chemistry in solution, and these features are unique for the crystal state host-guest chemistry of pillar[5]arenes.

Applications of Pillar[n]arene-Based Supramolecular Assemblies.

Macrocycles are an important player in supramolecular chemistry. In 2008, a new class of macrocycles, "pillar[n]arenes", were first discovered. Research efforts in the area of pillar[n]arenes have elucidated key properties, such as their shape, reaction mechanism, host-guest properties, and their versatile functionality, which has contributed to the development of pillar[n]arene chemistry and their applications to various fields. This Minireview describes how pillar[n]arene-based supramolecular assemblies can be applied to supramolecular gel formation, reactions, light-harvesting systems, drug-delivery systems, biochemical applications, separation and storage materials, and surface chemistry.

Photocontrolled Reversible Guest Uptake, Storage, and Release by Azobenzene-Modified Microporous Multilayer Films of Pillar[5]arenes.

Using the pillar-shaped architecture of pillar[5]arenes, we constructed microporous multilayer films with azobenzene groups on the top surface by layer-by-layer assembly of cationic and anionic pillar[5]arenes. Guest uptake, storage, and release by the microporous films were regulated through photoreversible isomerization of azobenzene groups attached to the pore outlets. Azobenzene was regarded as a "molecular valve" to control guest access: the trans form of the azobenzene acted as an open valve, allowing guest-free access from/to the micropores. Conversely, the cis form of the azobenzene behaved as a closed valve, completely blocking guest access from/to the micropores. Photoresponsive reversible uptake, storage, and release of guest molecules were demonstrated through photoisomerization of the azobenzene valves by irradiation with ultraviolet and visible light.

Spacer Length-Independent Shuttling of the Pillar[5]arene Ring in Neutral [2]Rotaxanes.

For a series of neutral [2]rotaxanes consisting of a pillar[5]arene ring and axles possessing two stations separated by flexible spacers of different lengths, the free energies of activation for the ring shuttling between the stations were found to be independent of the spacer length. The constitution of the spacer affects the activation energies: replacement of CH2 groups by repulsive oxygen atoms in the axle increases the barrier. The explanation for the observed length-independence lies in the presence of a barrier for re-forming the stable co-conformation, which makes the ring travel back and forth along the thread in an intermediate state.

Pillar-Shaped Macrocyclic Hosts Pillar[n]arenes: New Key Players for Supramolecular Chemistry.

In 2008, we reported a new class of pillar-shaped macrocyclic hosts, known as "pillar[n]arenes". Today, pillar[n]arenes are recognized as key players in supramolecular chemistry because of their facile synthesis, unique pillar shape, versatile functionality, interesting host-guest properties, and original supramolecular assembly characteristics, which have resulted in numerous electrochemical and biomedical material applications. In this Review, we have provided historical background to macrocyclic chemistry, followed by a detailed discussion of the fundamental properties of pillar[n]arenes, including their synthesis, structure, and host-guest properties. Furthermore, we have discussed the applications of pillar[n]arenes to materials science, as well as their applications in supramolecular chemistry, in terms of their fundamental properties. Finally, we have described the future perspectives of pillar[n]arene chemistry. We hope that this Review will provide a useful reference for researchers working in the field and inspire discoveries concerning pillar[n]arene chemistry.

Separation of Linear and Branched Alkanes Using Host-Guest Complexation of Cyclic and Branched Alkane Vapors by Crystal State Pillar[6]arene.

Activated crystals of pillar[6]arene produced by removing the solvent upon heating were able to take up branched and cyclic alkane vapors as a consequence of their gate-opening behavior. The uptake of branched and cyclic alkane vapors by the activated crystals of pillar[6]arene induced a crystal transformation to form one-dimensional channel structures. However, the activated crystals of pillar[6]arene hardly took up linear alkane vapors because the cavity size of pillar[6]arene is too large to form stable complexes with linear alkanes. This shape-selective uptake behavior of pillar[6]arene was further utilized for improving the research octane number of an alkane mixture of isooctane and n-heptane: interestingly, the research octane number was dramatically improved from a low research octane number (17 %) to a high research octane number (>99 %) using the activated crystals of pillar[6]arene.

An amphiphilic pseudo[1]catenane: neutral guest-induced clouding point change.

The hydrophobic/hydrophilic ratio in a molecule largely affects its assembled properties in aqueous media. In this study, we synthesized a new bicyclic compound which could dynamically change its hydrophobic/hydrophilic ratio by chemical stimulus. The bicyclic compound consisted of amphiphilic pillar[5]arene and hydrophobic alkyl chain rings, and formed a self-inclusion structure in aqueous media, which was assigned as a pseudo[1]catenane structure. The hydrophobic chain ring was hidden inside the pillar[5]arene cavity in the pseudo[1]catenane structure, thus the bicyclic compound was soluble in water at 20 °C with a clouding point at 24 °C. The pseudo[1]catenane was converted to the de-threaded structure upon addition of the neutral guest 1,4-dicyanobutane, which displaced the alkyl chain ring from the inside to the outside of the cavity. The hydrophobic alkyl chain ring was now exposed to the aqueous media, causing aggregation of the hydrophobic alkyl chain rings, which induced insolubilization of the bicyclic compound in aqueous media at 20 °C and a decrease in its clouding point.

Alkane-Shape-Selective Vapochromic Behavior Based on Crystal-State Host-Guest Complexation of Pillar[5]arene Containing One Benzoquinone Unit.

Colored crystals of pillar[5]arene containing one benzoquinone unit were found to exhibit alkane-shape-selective vapochromic behavior. Activated pillar[5]arene crystals, prepared by removing solvated methanol from pillar[5]arene crystals, changed color from dark-brown to light-red after exposure to linear alkane vapors; however, no color changes were observed on exposure to branched or cyclic alkanes. Uptake of methanol vapor by the activated crystals induced a different color change, from dark-brown to black. This multi-vapochromism results from the different intermolecular π-stacking interactions between the benzoquinone and 1,4-diethoxybenzene units in the alkane- and methanol-containing crystals. Unlike most known vapochromic materials, these pillar[5]arene-based materials were highly stable; after uptake of n-alkanes or methanol the color of the crystals did not change after storage in air for 3 weeks. This is because the included guests were stabilized in the cavity by multiple CH/π interactions.

Spherical Vesicles Formed by Co-Assembly of Cyclic Pentagonal Pillar[5]quinone with Cyclic Hexagonal Pillar[6]arene.

Mixing cyclic pentagonal pillar[5]quinone with cyclic hexagonal pillar[6]arene in a 12:20 molar feed ratio resulted in spontaneous production of vesicles, while assembly of pillar[6]arene and pillar[5]quinone alone produced hexagonal disks and wires, respectively. Incorporation of pentagonal pillar[5]quinone rings into hexagonal pillar[6]arene sheets gave curvature and contributed to the formation of vesicles. Conventional vesicles are generally synthesized by assembly of amphiphilic molecules containing hydrophobic and hydrophilic parts. Therefore, the co-assembly of pentagonal and hexagonal molecules to obtain spherical vesicles demonstrated in this study is a new concept based on geometric design.

Molecular Recognition with Microporous Multilayer Films Prepared by Layer-by-Layer Assembly of Pillar[5]arenes.

Pillar[5]arene-based multilayer films are constructed by layer-by-layer assembly with consecutive adsorption of cationic and anionic pillar[5]arenes. The films have active pores that allow shape-selective uptake of dinitrobenzene isomers: the film adsorbs para-dinitrobenzene, but not ortho- and meta-dinitrobenzene. The ability of the film to adsorb para-dinitrobenzene is result of the surface electrostatic potential: para-dinitrobenzene adsorbs on films with a positive surface, but not on films with a negative surface. The adsorbed amount of para-dinitrobenzene exponentially increases with increasing number of deposited layers.

Porous Carbon Fibers Containing Pores with Sizes Controlled at the Ångstrom Level by the Cavity Size of Pillar[6]arene.

We report a new synthesis method of fibrous carbon material with pores sizes that are precisely controlled at the Ångstrom level, by carbonization of two dimensional (2D) porous sheets of pillar[6]arenes. The 2D porous sheets were prepared by 2D supramolecular polymerization induced by oxidation of hydroquinone units of pillar[6]arenes. Owing to the hexagonal structure of pillar[6]arene, the assembly induced by 2D supramolecular polymerization gave hexagonal 2D porous sheets, and the highly ordered structure of the 2D porous sheets formed regular fibrous structures. Then, carbonization of the 2D porous sheets afforded fibrous carbon materials with micropores. The micropore size of the fibrous porous carbon prepared from pillar[6]arene was the same size as that of the starting material pillar[6]arene assembly.

Host-Guest Complexation of Perethylated Pillar[5]arene with Alkanes in the Crystal State.

Activated perethylated pillar[5]arene crystals show an unexpected alkane-shape- and -length-selective gate-opening behavior. Activated crystals were obtained upon removing solvents from perethylated pillar[5]arene crystals by heating. The activated crystals could quantitatively take up n-alkanes with carbon chains containing more than five carbon atoms as a consequence of their gate-opening pressure. As the chain length of the n-alkanes increased, the gate pressure decreased. A transformation into a herringbone structure was induced when n-hexane was used as a guest. By contrast, cyclic and branched alkanes were not taken up and could not induce a crystal transformation because they were too large to fit in the cavities of the pillar[5]arene. Alkane-shape-selective molecular recognition of pillar[5]arenes in the solution state was translated into the vapor/crystal state.

Acceptor-Induced Fluorescence of Phenolic Polymers Based on Triphenylamine Derivatives.

Conductive polymers facilitate the electrical current flow through the transfer of electrons and holes. They show promise for novel photo-functional materials in photovoltaics. However, substantial electrostatic interactions between electron donors and acceptors induce polymer aggregation, limiting moldability and conductivity. In this study, robust donor polymers with high heat resistance were synthesized by bonding triphenylamine (TPA) derivatives and formaldehyde to phenolic groups. Resulting TPA-based phenolic polymers exhibited flexible structures and fluorescence due to charge transfer with acceptor molecules. Furthermore, TPA-based phenolic polymers' capacity to distinguish acceptor molecule sizes correlated with their molecular weight, reflecting upon donor-acceptor interactions. This novel optical trait in phenolic polymers holds potential for electronic components and conductive materials.