Copper-Free Synthesis of Cationic Glycidyl Triazolyl Polymers.

Copper-free synthesis of cationic glycidyl triazolyl polymers (GTPs) is achieved through a thermal azide-alkyne cycloaddition reaction between glycidyl azide polymer and propiolic acid, followed by decarboxylation and quaternization of the triazole unit. For synthesizing nonfunctionalized GTP (GTP-H), a microwave-assisted method enhances the decarboxylation reaction of carboxy-functionalized GTP (GTP-COOH). Three variants of cationic GTPs with different N-substituents [N-ethyl, N-butyl, and N-tri(ethylene glycol) monomethyl ether (EG3)] are synthesized.

Gold nanowire mesh electrode for electromechanical device.

Ionic polymer-metal composite (IPMC) actuators were prepared with Nafion film as the ionic polymer and gold nanowire (Au-NW) mesh film as the metal electrodes by hot-pressing, which shortened preparation time within 1 h. As a reference, IPMC actuator consisting of Nafion film and gold foil (Au-foil) was also prepared. Au-NW mesh film can be an electrode with thinner (about 150 nm) and lower surface resistivity (about 0.

Poly(ionic liquid)s Based on Copolymers of Poly(ethylene oxide) and Cationic Glycidyl Triazolyl Polymers with Tribranched Side Chains.

Copolymers comprising poly(ethylene oxide) and cationic glycidyl triazolyl polymer with tribranched side chains (PEO--GTP·3X) were synthesized from glycidyl azide copolymer (PEO--GAP) and the tricationic alkyne. A synthetic route for the tricationic alkyne was also improved. Bis(trifluoromethanesulfonyl)imide (TFSI) and bis(fluorosulfonyl)imide (FSI) were used as counteranions.

Facile Synthesis of Tetra-Branched Tetraimidazolium and Tetrapyrrolidinium Ionic Liquids.

A facile synthetic route for tetra-branched tetraimidazolium and tetrapyrrolidinium ionic liquids was developed. In contrast to the previous synthetic scheme, the new synthetic route requires only three reaction steps instead of seven. The total yield of tetracation was also improved from 17-21 to 39-41%.

Redox-Responsive and Thermoresponsive Supramolecular Nanosheet Gels with High Young's Moduli.

Supramolecular gels made from 2D building blocks are emerging as one of the novel multifunctional soft materials for various applications. This study reports on a class of supramolecular nanosheet gels formed through a reversible self-assembly process involving both intramolecular folding and intermolecular self-assembly of poly[oligo(ethylene glycol)-co-(phenyl-capped bithiophenes)]. Such hierarchical self-assembled structure allows the gels to switch between sol and gel states under either redox or thermostimulus.

Glycidyl Triazolyl Polymers: Poly(ethylene glycol) Derivatives Functionalized by Azide-Alkyne Cycloaddition Reaction.

Glycidyl triazolyl polymer (GTP), which is the product of the Huisgen dipolar cycloaddition reaction between glycidyl azide polymer and alkyne derivatives, is featured here. GTP is the multifunctionalized poly(ethylene glycol) (PEG). The drawback of PEG is that linear PEG has the functional group only at both ends.

Stacked-Layer Heterostructure Films of 2D Thiophene Nanosheets and Graphene for High-Rate All-Solid-State Pseudocapacitors with Enhanced Volumetric Capacitance.

Stacked-layer heterostructure films of 2D thiophene nanosheets and electrochemically exfoliated graphene are constructed for ultrahigh-rate all-solid-state flexible pseudocapacitors and micro-supercapacitors with superior volumetric capacitance due to the synergetic effect of the ultrathin pseudocapacitive thiophene nanosheets and the capacitive electrochemically exfoliated graphene.

Control of optical and electrical properties of nanosheets by the chemical structure of the turning point in a foldable polymer.

Oligomers of tetra(ethylene glycol)-disubstituted phenyl-capped bithiophene (Ph2TPh) linked by catechol and resorcinol were prepared. Catechol and resorcinol link the monomers via the ortho- and meta-positions of the benzene ring, respectively, and function as turning points in the folding process of the polymer. It was confirmed that the ortho-linked 8mer (o-8mer) and meta-linked 8mer (m-8mer) could form nanosheets through the self-assembly of folded polymers in o-dichlorobenzene.

Effect of polymerization on hierarchical self-assembly into nanosheets.

The oligomers consisting of phenyl-capped bithiophene and tetra(ethylene glycol)s linked by azide-alkyne Huisgen cycloaddition were synthesized. The relationship between the degree of polymerization and self-assembling ability was investigated in o-dichlorobenzene and dimethyl sulfoxide. From the absorption spectrum, it was confirmed that the critical degree of polymerization (CDP) for thiophene unit aggregation was 4.

Electrochemically durable thiophene alkanethiol self-assembled monolayers.

Thiophene-based redox-active self-assembled monolayers (SAMs) were prepared on gold substrates. The alkanethiol derivatives of 1TPh-OC12SH and ETPh-OC12SH contain thiophene (1T) and 3,4-ethylenedioxythiophene (ET) units, respectively, with unprotected (nonsubstituted) thiophene α-carbons. PhETPh-OC12SH contains the ET unit, and all thiophene carbons are protected.

Electrochromic properties of polythiophene polyrotaxane film.

The electrochromic properties of a polythiophene polyrotaxane film consisting of a polythiophene backbone wrapped by the tetra-cationic cyclophane, cyclobis(paraquat-p-phenylene), were characterized. A naked reference polythiophene film, i.e.

Molecular motion of surface-immobilized double-decker phthalocyanine complexes.

The molecular motion of surface-immobilized double-decker phthalocyanine complexes was examined using STM. (C(8)OPc)(2)Ce (1), (C(12)OPc)(2)Ce (2), and (C(8)OPc)Ce(Pc) (3) double-decker complexes, of which two ligands contained Pc nuclei, formed well-ordered self-organized structures on their own. Square-shaped top Pc ligands were clearly observed for complexes 1, 2, and 3 even though free space presented around the top ligands caused by mixing the complexes with template molecules.

Thermodynamic forecasting of mechanically interlocked switches.

Mechanically interlocked molecular (MIM) switches in the form of bistable [2]rotaxanes and [2]catenanes have proven to be--when incorporated in molecular electronic devices (MEDs) and in nanoelectromechanical systems (NEMS)--a realistic and viable alternative to the silicon chip density challenge. Structural modifications and chemical environment can have a large impact on the relaxation thermodynamics of the molecular motions, such as translation and circumrotation in bistable rotaxanes and catenanes responsible for the operation of devices based on MIMs. The effects of structural modifications on the difference in free energy (DeltaG(o)) for the equilibrium processes in switchable MIMs can be predicted by considering, firstly, the interactions present in their precursor pseudorotaxanes.

From thiophene [2]rotaxane to polythiophene polyrotaxane.

The polythiophene polyrotaxane was synthesized through electrochemical polymerization of the [2]rotaxane consisting of the electron-rich dumbbell-shaped sexithiophene and the electron-deficient cyclophane of cyclobis(paraquat-p-phenylene). The optical and electrochemical property of the polythiophene polyrotaxane film was characterized. The material reported herein is attractive not only as a component for constructing the macromolecular machine but also as a new type of insulated molecular wire having donor-acceptor interaction between the macrocycle and the conductive polymer.

Beta-substituted terthiophene [2]rotaxanes.

Two kinds of beta-substituted terthiophene [2]rotaxanes were synthesized using the host-guest pairs of the electron-deficient cyclophane cyclobis(paraquat-p-phenylene) (CBPQT(4+)) and the electron-rich terthiophenes with diethyleneglycol chains at the beta-position. One is made from the alpha-position non-substituted terthiophene (3 T-beta-Rx) and the other is made from the alpha-dibromo-substituted terthiophene (3 TBr-beta-Rx). The binding constants of the beta-substituted terthiophene threads were confirmed to be smaller than that of the alpha-substituted terthiophene analogue.

A bistable poly[2]catenane forms nanosuperstructures.

Side-chain poly[2]catenanes at the click of a switch! A bistable side-chain poly[2]catenane has been synthesized and found to form hierarchical self-assembled hollow superstructures of nanoscale dimensions in solution. Molecular electromechanical switching (see picture) of the material is demonstrated, and the ground-state equilibrium thermodynamics and switching kinetics are examined as the initial steps towards processible molecular-based electronic devices and nanoelectromechanical systems.

Scanning tunneling microscopy observation of self-assembled monolayers of strapped porphyrins.

In this paper, we reveal that the free-base and zinc strapped porphyrins possessing long alkyl chains, C 24OPP-HQ and Zn(C 24OPP-HQ), respectively, can be arranged on surfaces. We used scanning tunneling microscopy (STM) to observe alkyl-chain-assisted self-assembled monolayers (SAMs) of these strapped porphyrins at the solid-liquid interface. STM images revealed that the strapped benzene moiety was detectable on the porphyrin core: that is, the strapped porphyrins could be differentiated from nonstrapped analogues.

Thiophene donor-acceptor [2]rotaxanes.

A series of the thiophene donor-acceptor [2]rotaxanes have been synthesized based on the inclusion complexes of cyclobis(paraquat- p-phenylene) (CBPQT4+) with thiophene, bithiophene, and terthiophene. The maximum wavelength of the charge-transfer band strongly depends on the number of thiophene units, while the association constant does not. These donor-acceptor pairs will be fascinating constituents for optoelectronic and electromechanical materials.

Alkyl chain length dependence of the self-organized structure of alkyl-substituted phthalocyanines.

The alkyl chain length on alkyl-substituted phthalocyanines (C(n)OPc) dependence of their self-organized structures was examined in this study. STM results indicated that the symmetry of ordered structures decreased as the alkyl chain became longer, with the exception of C(6)OPc, which preferentially formed a quasi-3-fold symmetrical structure. This could be explained by the fact that the C(n)OPc molecules are most likely to form densely packed structures.

Electrochromic materials using mechanically interlocked molecules.

Recent investigations on the design and synthesis of electrochromic materials based on switchable three-station [2]catenanes are summarized. The reasoning and preliminary experiments behind the design of electrochemically controllable red-green-blue (RGB), donor-acceptor [2]catenanes are presented. A basis for color generation is discussed in which the tetracationic cyclophane, cyclobis(paraquat--phenylene), serves as the π-electron deficient ring which circumrotates between three π-electron rich recognition sites within a macrocyclic polyether, generating the three different colors (RGB) based on the different charge transfer interactions between the tetracationic cyclophane and recognition sites based on 1,5-dioxynaphthalene (R), tetrathiafulvalene (G) and benzidine (B).

Toward electrochemically controllable tristable three-station [2]catenanes.

Encouraged by the prospect of producing an electrochemical, color-switchable red-green-blue (RGB) dye compound, we have designed, synthesized, and characterized two three-station [2]catenanes. Both are composed of macrocyclic polyethers containing three pi-electron-rich stations, which act as recognition sites for a pi-electron-deficient tetracationic cyclophane. The molecular structures of the two three-station [2]catenanes were characterized fully by mass spectrometry and 1H NMR spectroscopy.

Blue-colored donor-acceptor [2]rotaxane.

[reaction: see text] A guest molecule-a bis-N-tetraethyleneglycol-substituted 3,3'-difluorobenzidine derivative-has been synthesized, and its complexation with the host, cyclobis(paraquat-p-phenylene), has been investigated. This host-guest complex was then employed in the template-directed synthesis of a blue-colored [2]rotaxane. The color of this [2]rotaxane arises from the charge-transfer absorption band between the HOMO of the guest and the LUMO of the host.

A clicked bistable [2]rotaxane.

[structure: see text]. A universal diazide-terminated polyether, incorporating tetrathiafulvalene (TTF, green) and 1,5-dioxynaphthalene (DNP, red) units, was prepared and subsequently employed in the template-directed synthesis of a switchable donor/acceptor [2]rotaxane. The triazole rings (magenta), which are introduced into the rotaxane during requisite click reactions, do not present themselves as competing recognition sites for the tetracationic cyclophane (blue) as it is induced to switch between the TTF unit, when it becomes dicationic (green adorned with yellow extremities), and the DNP unit.