Polyurethane-Type Poly[3]rotaxanes Synthesized from Cyclodextrin-Based [3]Rotaxane Diol and Diisocyanates.

Synthesis of polyurethane-type poly[3]rotaxanes is achieved by polyaddition between a cyclodextrin (CD)-based [3]rotaxane diol and various diisocyanate species, which provide a more defined structure compared to conventional polyrotaxane syntheses. In this study, hydroxyl groups on CDs of [3]rotaxane diol are initially acetylated, and deprotected after the polyaddition to introduce polyurethane backbone structure into polyrotaxane framework. Despite a relatively complicated chemical structure, [3]rotaxane diol monomer is successfully synthesized in a high yield (overall 67%) without any taxing purification process, which is beneficial for practical applications. The polymerization itself proceeds well under a standard polyaddition reaction condition to afford corresponding polyurethanes around 80% yield with Mn > 30 kDa. The poly[3]rotaxanes show different aggregation behavior or optical properties, whether or not acetyl groups are present, and are analyzed by XRD, SEM, and fluorescence measurements.

From Squaric Acid Amides (SQAs) to Quinoxaline-Based SQAs─Evolution of a Redox-Active Cathode Material for Organic Polymer Batteries.

The search for new redox-active organic materials (ROMs) is essential for the development of sustainable energy-storage solutions. In this study, we present a new class of cyclobuta[b]quinoxaline-1,2-diones or squaric acid quinoxalines (SQXs) as highly promising candidates for ROMs featuring exceptional stability and high redox potentials. While simple 1,2- and 1,3-squaric acid amides (SQAs), initially reported by Hünig and coworkers decades ago, turned out to exhibit low stability in their radical cation oxidation states, we demonstrate that embedding the nitrogen atoms into a quinoxaline heterocycle leads to robust two-electron SQX redox systems. A series of SQX compounds, as well as their corresponding radical cations, were prepared and fully characterized, including EPR spectroscopy, UV-vis spectroscopy, and X-ray diffraction. Based on the promising electrochemical properties and high stability of the new ROM, we developed SQX-functionalized polymers and investigated their physical and electrochemical properties for energy-storage applications. These polymers showed remarkable thermal stability well above 200 °C with reversible redox properties and potentials of about 3.6 V vs Li+/Li. By testing the galvanostatic cycling performance in half-cells with lithium-metal counter electrodes, a styrene-based polymer with SQX redox side groups showed stable cycling for single-electron oxidation for more than 100 cycles. These findings render this new class of redox-active polymers as highly promising materials for future energy-storage applications.

Aggregation Behavior of Cyclodextrin-Based [3]Rotaxanes.

The aggregation of a cyclodextrin (CD)-based [3]rotaxane has been observed and analyzed in detail for the first time in this work. Although the hexagonal packing aggregation of CD-based polyrotaxane is a well known phenomenon, corresponding studies in terms of rotaxanes without any polymer structure have not been conducted so far, probably owing to the difficulty of the molecular design. We synthesized a series of [3]rotaxane species by using a urea-end-capping method and evaluated their aggregation behavior by XRD and SEM measurements. [3]Rotaxane species containing native CD rings showed clear signals assigned to the hexagonal packing by XRD measurement as did polyrotaxane; this proved their aggregation capability. Because the corresponding per-acetylated derivatives did not show this aggregation behavior, the driving force of this aggregation was suggested to be hydrogen bond formation among CD units. The effect of axle end structures and partial acetylation of CDs were also studied.

Photoresponsive Spiropyran and DEGMA-Based Copolymers with Photo-Switchable Glass Transition Temperatures.

Herein, novel photoresponsive spiropyran (SP)-based P(DEGMA-co-SpMA) copolymers with variable percentages of SP fractions are synthesized. The SP group present in these polymers exhibited the abilities of reversible photoisomerism. Their photoresponsive, structural, and thermal properties have been investigated and compared using various characterization techniques. These light-responsive copolymers are found to exhibit photoswitchable glass transition temperature (Tg ), high thermal stability (Td > 250°C), instant photochromism as well as fluorescence upon exposure to UV light. It is demonstrated that the Tg of these synthesized polymers increased when irradiated with UV light (λ = 365 nm), as a consequence of the photoisomerization of incorporated SP groups into their merocyanine form. This increase in Tg is attributed to an increase in polarity and a decrease in the overall entropy of the polymeric system when it switches from the ring-closed SP form (less-ordered state) to the ring-opened merocyanine form (more-ordered state). Therefore, such polymers with a unique feature of phototunable glass transition temperatures provide the possibility to be integrated into functional materials for various photoresponsive applications.

The Effect of the Axle End Structure and Number of Through-Space Bonds on the Properties of Rotaxane Crosslinked Polymers.

A rotaxane crosslinker (RC) is known to toughen the resulting rotaxane crosslinked polymer (RCP) via a stress dispersion effect that is attributed to the movable nature of the crosslinking structure. To evaluate this toughening mechanism in detail, a series of structure-definite RCs equipped with different axle end structures or different numbers of wheel components were synthesized, and subjected to free radical polymerization with a vinyl monomer to obtain RCPs. Analyses of the obtained RCPs revealed that the size of the axle end structure should be well-balanced to produce a strong toughening effect, and a [3]rotaxane crosslinker works more effectively than [2]rotaxane to toughen RCPs. The mobility of the crosslinking points, in terms of rotational and flipping movements, was more crucial to toughening the RCP than that of translational movement along the axle. The first observation of the above crucial findings proved the utility of the systematic molecular design used in this study.

Synthesis of a Structure-Definite α-Cyclodextrin-Based Macromolecular [3]Rotaxane Using a Size-Complementary Method.

The challenging synthesis of an α-cyclodextrin (CD)-based macromolecular rotaxane with definite structure was fulfilled using a size-complementary method. A new peracetylated (PAc) α-CD-based size-complementary [3]rotaxane was prepared and its thermal dissociation kinetics studied. The de-slippage mechanism was found to be different from that of the native α-CD-based system. PAcα-CD-based size-complementary [3]rotaxanes were employed as initiators for a ring-opening polymerization of ϵ-caprolactone to obtain the macromolecular [3]rotaxanes. Detailed investigation of component dissociation showed the highly movable character of the wheel on the polymer main chain. A general method for controlling the movement of wheels in rotaxane frameworks, even in polymer systems, was established. This will enable the development of new supramolecular architectures and molecular machines.

Cyclodextrin-Based [3]Rotaxane-Crosslinked Fluorescent Polymer: Synthesis and De-Crosslinking Using Size Complementarity.

Vinyl-group-substituted, α-cyclodextrin-based, size-complementary [3]rotaxanes were synthesized as crosslinkers for rotaxane-crosslinked poly(methyl methacrylate) (RCP) by radical polymerization. The size complementarity of the crosslinkers made it possible to de-crosslink the RCP by heating, and the degree of decoupling was monitored by fluorescence intensity, depending on the state of the axle component of the rotaxane crosslink moiety.

Structural Analysis and Inclusion Mechanism of Native and Permethylated α-Cyclodextrin-Based Rotaxanes Containing Alkylene Axles.

Native α-cyclodextrin- (α-CD) and permethylated α-CD (PMeCD)-based rotaxanes with various short alkylene chains as axles can be synthesized through a urea end-capping method. Native α-CD tends to form [3]- or [5]pseudorotaxanes and not [2]- or [4]pseudorotaxanes, which indicates that the coupled CDs act as a single fragment. End-capping reactions of the pseudorotaxanes with C18 and C24 axle lengths do not occur because the axle termini are covered by the densely stacked CDs. The number of PMeCDs on the pseudorotaxane is flexible and mainly depends on the axle length. Peracetylated α-CD (PAcCD)-based rotaxanes are synthesized through O-acetylation of the α-CD-based rotaxanes without any decomposition of the rotaxanated structures. The structures of PMeCD-based [3]- and [4]rotaxanes, and the molecular dynamics calculations on [3]pseudorotaxanes, indicate that the tail face of PMeCDs is regularly directed toward the axle termini. On the basis of the results obtained, it can be concluded that the directions and numbers of CDs in rotaxanes containing short alkylene chains depend on 1) the interactions between CDs, 2) the length of the alkylene axle, and 3) the interactions between the axle end and tail face of the CD.

Cyclodextrin-based size-complementary [3]rotaxanes: selective synthesis and specific dissociation.

α-Cyclodextrin (CD)-based size-complementary [3]rotaxanes with alkylene axles were prepared in one-pot by end-capping reactions with aryl isocyanates in water. The selective formation of [3]rotaxane with a head-to-head regularity was indicated by the X-ray structural analyses. Thermal degradation of the [3]rotaxanes bearing appropriate end groups proceeded by stepwise dissociation to yield not only the original components but also [2]rotaxanes. From the kinetic profiles of the deslippage, it turned out that the maximum yield of [2]rotaxane was estimated to be 94 %. Thermodynamic studies and NOESY analyses of such rotaxanes revealed that [2]rotaxanes are specially stabilized, and that the dissociation capability of the [3]rotaxanes to the components can be adjusted by controlling the structure of the end groups, direction of the CD groups, and length of the alkylene axle.

Unsaturated polyurethanes degradable by conjugate substitution reactions with amines and carboxylate anions.

Main-chain scission of polymers induces a significant decrease in molecular weight and accompanying changes in physical properties and is important for applications in materials engineering, such as in photoresists and adhesive dismantling. In this study, we focused on methacrylates substituted with carbamate groups at the allylic positions for the purpose of developing a mechanism that efficiently cleaves the main chain in response to chemical stimuli. Dimethacrylates substituted with hydroxy groups at the allylic positions were synthesized by the Morita-Baylis-Hillman reaction of diacrylates and aldehydes. The polyaddition with diisocyanates afforded a series of poly(conjugated ester-urethane)s. These polymers underwent a conjugate substitution reaction with diethylamine or acetate anion at 25 °C, resulting in main-chain scission accompanied by decarboxylation. A side reaction by the re-attack of the liberated amine end to the methacrylate skeleton proceeded, whereas it was suppressed for the polymers with an allylic substitute of the phenyl group. Therefore, the methacrylate skeleton substituted with phenyl and carbamate groups at the allylic position is an excellent decomposition point that induces selective and quantitative main-chain scission with weak nucleophiles, such as carboxylate anions.

Selective synthesis of a [3]rotaxane consisting of size-complementary components and its stepwise deslippage.

An α-cyclodextrin-based size-complementary [3]rotaxane with an alkylene axle was selectively synthesized in one pot via an end-capping reaction with 2-bromophenyl isocyanate in water. Thermal degradation of the [3]rotaxane product yielded not only the original components but also the [2]rotaxane. Thermodynamic studies suggested a stepwise deslippage process.