Construction of supramolecular polymers, in which functional monomer components are held together by noncovalent interactions, is considered as a promising design principle for functional materials. Linear fluorescent supramolecular polymer assembled on account of electrostatic attractions based host-guest interaction is synthesized and illustrated here. 1H NMR was involved to ensure the structure of guest and polymer, UV–vis and fluorescent spectra were recorded to be a readout signal to investigate the assemble process of polymer. TEM and AFM measurements were carried out to confirm the homogeneous nanometer-sized molecular assembly. It shows the way to be used as remote readout fluorescent functional material in the future.

ABSTRACTThe branched triazole group is synthesized by click chemistry via a controlled approach of slow addition of AB2 compound to a B2 core, and used as the substituent for 1,6-heptadiyne monomer. Metathesis cyclopolymerization of monomer is performed well in dichloromethane without the weakly coordinating additive, indicating that the branched triazole itself can stabilize the living propagating chain, to generate branched triazole pendant-contained polyacetylene with trans-double bonds and five-membered ring repeating units along the conjugated backbone. The LiTFSI doped polyacetylenes display ionic conductivities of 2.5–1.8 × 10−6 S cm−1; by further doping with iodine, polyacetylenes show the improved ionic and electronic conductivities of 1.3 × 10−5 and 2.1 × 10−7 S cm−1 at 30 °C, respectively. Therefore, these doped polyacetylenes may act as the new electrolyte materials. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017, 55, 485–494

A block copolymer consisting of functional polynorbornene (PNBE) and polyacetylene (PA) segments was synthesized by tandem metathesis polymerization, and self-assembled into a superhelical nanotube morphology from achiral building blocks. Bearing insulated PNBE and conductive PA segments with unique nanostructures, the block copolymers displayed high dielectric permittivities of 25–29, low dielectric losses of 0.03–0.04, and excellent stored/released energy densities of 2.0–1.9/1.7–1.2 J cm−3 under the breakdown fields of 270–200 MV m−1, due to strong dipolar and nanointerfacial polarizations as well as stereoregular chain microstructure contributions. This strategy provided a new way for the development of advanced nanodielectric materials.

A series of dendronized polyacetylenes with trans-double bond and five-membered ring backbones were prepared by metathesis cyclopolymerization. The dendronized polymers had good thermal stability with a highest decomposition temperature of 330 °C, and excellent electrochemical stability with a broad electrochemical stability window of 6.0 V. Meanwhile, the flexibility of the dendronized pendants make the polymers have a rigid conjugated backbone exhibiting a lowest glass transition temperature of −22.2 °C. After doping with different ratios of LiTFSI, the ionic conductivity of the polymers was higher than that of their intrinsic ones, and the highest ionic conductivity of the polymers reached 4.3 × 10−6 S cm−1 at 30 °C.

A series of novel hyperbranched poly(triazolium)s with different terminal groups were synthesized by alkylation and anion exchange reactions of the corresponding hyperbranched poly(triazole)s, which were obtained from an AB2-type monomer via Cu(I)-catalyzed azide–alkyne cycloaddition polymerization. The hyperbranched poly(triazolium)s showed high thermal stability with decomposition temperatures of 328–361 °C, and good flexibility, with glass transition temperatures (Tg) ranging from −6.2 to −14.9 °C. Among them, an oligo(ethylene glycol)-terminated hyperbranched poly(triazolium) presented the lowest Tg of −14.9 °C, the highest ionic conductivity (7.70 × 10−6 S cm−1 at 30 °C and 1.02 × 10−3 S cm−1 at 110 °C) and a wide electrochemical stability window of 6.0 V. Therefore, these hyperbranched poly(triazolium)s could act as new electrolyte materials.

•A linear supramolecular polymer with responsiveness capability to two orthogonal stimuli was constructed.•Reversible light- and redox-driven disassemble/reassemble process of the polymer has been clarified.•Based on the naked eye recognized light responsive process, it can be used as information protection material and stimuli responsive device.Bottom-up fabrication of functional supramolecular systems from discrete molecular building blocks is a flourishing endeavor in contemporary science and nanotechnology. Here we present the synthesis and reversible disassembly and reassembly of adual-stimuli responsive linear supramolecular polymer constructed by host-guest molecular recognition. The formation of the supramolecular polymer is driven by exceptional selective complexation property of azobenzene with β-cyclodextrin and 4,4´-bipyridinium with sulfonatocalix[4]arene, which ensures the polymer’s controlled and orthogonal responsiveness to light irradiation and redox process. The supramolecular polymerization was confirmed by 1H NMR spectroscopy, dynamic light scattering (DLS) measurement, atomic force microscopy (AFM), and transmission electron microscopy (TEM), and its reversible photo and redox dual-responsive disassembly and reassembly behavior was as certained by UV–vis absorption spectra, cyclic voltammetry (CV), and TEM. This is the first example of a supramolecular polymer capable of reversible disassembly and reassembly driven by light and redox process, involving solely non-covalent orthogonal molecular recognition, which can be recognized by naked eyes.

•A series of poly(norbornene-dicarboximide)s were synthesized by ROMP.•Introducing various acceptors to tricarbazole can achieve different color emission.•The HOMO levels of polymers are close to the most common hole injection materials.•The LUMO level of polymer with the cyano group is very close to the material of Alq3.•Polymers possess high thermal stability with decomposition temperature over 400 °C.A series of poly(norbornene-dicarboximide)s with donor–acceptor pendants were synthesized by ring-opening metathesis polymerization, and their photophysical and thermal properties have been investigated. By linking different electron-withdrawing groups to electron-donating tricarbazole on the side chain of poly(norbornene) backbone, the polymers displayed various fluorescence emission color as purplish blue (418 nm), greenish blue (489 nm), green (515 nm), and orange yellow (594 nm). The fluorescence quantum yield of polymer bearing tricarbazole-aldehyde group in CHCl3 was reached to 0.42. The highest occupied molecular orbital level of polymers was close to −5.3 eV, and the lowest unoccupied molecular orbital varied between −2.34 and −3.02 eV. All polymers exhibited high thermal stability with decomposition temperature exceeding 400 °C.

A new type of insulating–conductive block copolymer was synthesized by metathesis polymerization. The copolymer can self-assemble into unique nanostructures of micelles or hollow spheres. It exhibits a high dielectric constant, low dielectric loss, and high stored/released energy density due to the strong dipolar and nano-interfacial polarization contributions.

Linear supramolecular polymer with photo-responsive morphology was constructed by host-guest molecular recognition between bis-p-sulfonatocalix[4]arenes and monomer containing axially 1,1′-binaphthyl and photoresponsive azobenzene moieties in water. The successful supramolecular polymerization by non-covalent host-guest molecular recognition was confirmed. Scanning electron microscopy, cryogenic transmission electron microscopy and atomic force microscopy measurements were used to investigate its light driven behavior and line morphology change from straight to bent. Its noteworthy light driven morphology change from straight to bent make it possible to envision its' usage as molecular machine based display material in the same way as bent-core liquid crystal material used in technology.

•Novel hyperbranched polymers consisting of hybrid triazolium and quaternary ammonium ions are synthesized.•They have higher ionic conductivity above 10−5 S cm−1 at 30 °C than that of similar polymers containing solely triazolium.•Therefore, this type of hyperbranched polymers could act as the new polyelectrolyte materials in energy device applications.Hyperbranched poly(triazole) with tertiary amine moiety and longer flexible polyethylene glycol (PEG) terminal group (hb-PTA-PEG) was synthesized by successive Cu(I)-catalyzed azide-alkyne cycloaddition polymerization, and the corresponding hyperbranched poly(triazolium)s containing hybrid quaternary ammonium ion, [hb-PTA-PEG]+[I]− and [hb-PTA-PEG]+[TFSI]−, were obtained after N-alkylation and anion exchange reactions. These hyperbranched polymers presented broad electrochemical stability window of above 6.0 V versus Ag+/Ag and 5.3 V versus Li+/Li, and displayed low glass transition temperature in the range of −13 to −37 °C, owing to the hyperbranched structure combined with the hybrid ionic moiety and longer flexible PEG end-group. The ionic [hb-PTA-PEG]+[TFSI]− showed superior ionic conductivity, which was above 10−5 S cm−1 at 30 °C.Download high-res image (156KB)Download full-size image

A new type of insulating–conductive block copolymer was synthesized by metathesis polymerization. The copolymer can self-assemble into unique nanostructures of micelles or hollow spheres. It exhibits a high dielectric constant, low dielectric loss, and high stored/released energy density due to the strong dipolar and nano-interfacial polarization contributions.