Spirobifluorene-BINOL-based microporous polymer nanoreactor for efficient 1H-tetrazole synthesis and iodine adsorption with facile charge transfer.

Porous polymeric nanoreactors capable of multitasking are attractive and require a judicious design strategy. Herein, we describe an unusual approach for the synthesis of a porous polymer SBF-BINOL-6 by in situ formation of the BINOL entity taking substituted naphthols and spirobifluorene as co-monomers with high yield (81%). The as-synthesized polymer exhibited nanotube and nanosphere-like morphology, thermal endurance up to 372 °C and a BET surface area as high as 590 m2 g-1. The polymer endowed efficient loading of silver nanoparticles to generate Ag@SBF6, as confirmed from X-ray photoelectron spectroscopy and high-resolution transmission electron microscopy. Ag@SBF6 was effectively used as a heterogeneous catalyst towards the [3 + 2] dipolar cycloaddition reaction for the synthesis of biologically important 5-substituted 1H-tetrazoles with yields in the range of 75-99% and recyclability for at least seven times without a significant decline in its catalytic efficiency. Additionally, a superior host-guest interaction by the polymer offered iodine adsorption in the vapour phase with a high uptake capacity of up to 4.0 g g-1. Interestingly, the iodine-loaded polymer, I2@SBF6, demonstrated iodine-promoted increased conductivity (1.3 × 10-3 S cm-1) through facile charge transfer interactions.

Main-Chain Cationic Polyelectrolytes: Design, Synthesis, and Applications.

Polyelectrolytes have attracted a lot of attention spanning across disciplines, including polymer chemistry, materials chemistry, chemical biology, chemical engineering, as well as device physics, as a result of their widespread applications in sensing, biomedicine, food industry, wastewater treatment, optoelectronic devices, and renewable energy. In this review, we focus on the crucial synthetic strategies of structurally different classes of main-chain cationic polyelectrolytes. As a result of the presence of charged moieties in the main polymeric backbone, their solubility and photophysical properties can be easily tuned. Main-chain cationic polyelectrolytes provide various unique characteristics, including solubility in aqueous and organic solvents, easy processability, ease of film formation, ionic interaction, main-chain-directed charge transport, high conductivity, and aggregation. These properties make the main-chain polyelectrolyte a potential candidate for numerous applications ranging from chemo- and biosensing, antibacterial activity, optoelectronics, electrocatalysis, water splitting, ion conduction, to dye-sensitized solar cells.

Triphenylamine-anthraquinone based donor-acceptor conjugated microporous polymers for photocatalytic hydroxylation of phenylboronic acids.

Triphenylamine-based donor-acceptor conjugated microporous polymers, namely PTPA-AQ and PTPA-AM, were synthesized for the first time via Suzuki-Miyaura coupling of tris(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-amine as a donor with 2,6-dibromoanthracene-9,10-dione and 2,2'-(2,6-dibromoanthracene-9,10-diylidene)dimalononitrile acceptors for efficient visible-light driven oxidative hydroxylation of various phenylboronic acids. The dimalononitrile derivative having greater acceptor ability showed tunable photophysical properties of PTPA-AM (lower band gap of 1.47 eV and better exciton separation efficiency) as well as porosity (lower Brunauer-Emmett-Teller (BET) surface area of 43 m2 g-1). PTPA-AQ having higher BET surface area (400 m2 g-1), suitable HOMO-LUMO positions and an optimal band gap (1.94 eV) showed better photocatalytic activity for the hydroxylation with yields up to 96%.

Phosphate based new organic polymer networks for efficient dye sorption and catalyst loading for chemo-selective reactivity.

Phosphate based organic polymer networks (OPNs) have been synthesized for the first time for dye sorption and heterogeneous catalysis. The OPNs were sythesized by the polycondensation of POCl3 with di- and tri-hydroxy organic linkers e.g., quinol, 4,4'-biphenol, phloroglucinol and 1,3,5-(4-hydroxyphenyl)benzene. These show remarkably selective adsorption of cationic dyes methylene blue and propidium iodide via the electrostatic interaction of the polymers with the dyes. These OPNs also allow the in situ synthesis and stabilization of gold nanoparticles within the polymer networks which demonstrate effective heterogeneous, catalytic reduction of the aromatic nitro to amino group.

Stretchable and Self-Healable Conductive Hydrogels for Wearable Multimodal Touch Sensors with Thermoresponsive Behavior.

Multifunctional hydrogels with properties including transparency, flexibility, self-healing, and high electrical conductivity have attracted great attention for their potential application to soft electronic devices. The presence of an ionic species can make hydrogels conductive in nature. However, the conductivity of hydrogels is often influenced by temperature, due to the change of the internal nano/microscopic structure when temperature reaches the sol-gel phase transition temperature. In this regard, by introducing a novel surface-capacitive sensor device based on polymers with lower critical solution temperature (LCST) behavior, near-perfect stimulus discriminability of touch and temperature may be realized. Here, we demonstrate a multimodal sensor that can monitor the location of touch points and temperature simultaneously, using poly(N-isopropylacrylamide) (PNIPAAm) in hybrid poly(vinyl alcohol) (PVA) and sodium tetraborate decahydrate cross-linked hydrogels doped with poly(sodium acrylate) (SA) [w/w/w = 5:2.7:1-3]. This multimodal sensor exhibits a response time of 0.3 s and a temperature coefficient of resistance of -0.58% K-1 from 20 to 40 °C. In addition, the LCST behavior of PNIPAAm-incorporated PVA/SA gels is investigated. Incorporation of LCST polymers into high-end hydrogel systems may contribute to the development of temperature-dependent soft electronics that can be applied in smart windows.

Organic n-Channel Transistors Based on [1]Benzothieno[3,2- b]benzothiophene-Rylene Diimide Donor-Acceptor Conjugated Polymers.

Improving the charge-carrier mobility of conjugated polymers is important for developing high-performance, solution-processed optoelectronic devices. Although [1]benzothieno[3,2- b]benzothiophene (BTBT) has been frequently used as a high-performance p-type small molecular semiconductor and employed a few times as a building block for p-type conjugated polymers, it has never been explored as a donor moiety for high-performance n-type conjugated polymers. Here, BTBT has been conjugated with either n-type perylene diimide (PDI) or naphthalene diimide (NDI) units to generate a donor-acceptor copolymer backbone, for the first time. Charge-transport measurements of organic field-effect transistors show n-type dominant behaviors, with the electron mobility reaching ∼0.11 cm2 V-1 s-1 for PDI-BTBT and ∼0.050 cm2 V-1 s-1 for NDI-BTBT. The PDI-BTBT mobility value is one of the highest among the PDI-containing polymers. The high π-π stacking propensity of BTBT significantly improves the charge-carrier mobility in these polymers, as supported by atomic force microscopy and grazing incidence X-ray diffraction analyses. Phototransistor applications of these polymers in the n-type mode show highly sensitive photoresponses. Our findings demonstrate that incorporation of the BTBT donor unit within the rylene diimide acceptor-based conjugated polymers can improve the molecular ordering and electron mobility.

One-step synthesis of a cyclic 2,17-dioxo[3,3](4,4') biphenylophane and first preparation of a microporous polymer network from a macrocyclic precursor by cyclotrimerization.

One-step synthesis of a cyclic 2,17-dioxo[3,3](4,4')biphenylophane (MC) was achieved in high yield; its structure was verified by single crystal X-ray analysis. As a first example, a microporous polymer network was formed from macrocycle MC via acid-catalysed cyclotrimerization yielding a BET surface area of ca. 570 m(2) g(-1).

Conjugated polymer-assisted dispersion of single-wall carbon nanotubes: the power of polymer wrapping.

The future application of single-walled carbon nanotubes (SWNTs) in electronic (nano)devices is closely coupled to the availability of pure, semiconducting SWNTs and preferably, their defined positioning on suited substrates. Commercial carbon nanotube raw mixtures contain metallic as well as semiconducting tubes of different diameter and chirality. Although many techniques such as density gradient ultracentrifugation, dielectrophoresis, and dispersion by surfactants or polar biopolymers have been developed, so-called conjugated polymer wrapping is one of the most promising and powerful purification and discrimination strategies. The procedure involves debundling and dispersion of SWNTs by wrapping semiflexible conjugated polymers, such as poly(9,9-dialkylfluorene)s (PFx) or regioregular poly(3-alkylthiophene)s (P3AT), around the SWNTs, and is accompanied by SWNT discrimination by diameter and chirality. Thereby, the π-conjugated backbone of the conjugated polymers interacts with the two-dimensional, graphene-like π-electron surface of the nanotubes and the solubilizing alkyl side chains of optimal length support debundling and dispersion in organic solvents. Careful structural design of the conjugated polymers allows for a selective and preferential dispersion of both small and large diameter SWNTs or SWNTs of specific chirality. As an example, with polyfluorenes as dispersing agents, it was shown that alkyl chain length of eight carbons are favored for the dispersion of SWNTs with diameters of 0.8-1.2 nm and longer alkyls with 12-15 carbons can efficiently interact with nanotubes of increased diameter up to 1.5 nm. Polar side chains at the PF backbone produce dispersions with increased SWNT concentration but, unfortunately, cause reduction in selectivity. The selectivity of the dispersion process can be monitored by a combination of absorption, photoluminescence, and photoluminescence excitation spectroscopy, allowing identification of nanotubes with specific coordinates [(n,m) indices]. The polymer wrapping strategy enables the generation of SWNT dispersions containing exclusively semiconducting nanotubes. Toward the applications in electronic devices, until now most applied approach is a direct processing of such SWNT dispersions into the active layer of network-type thin film field effect transistors. However, to achieve promising transistor performance (high mobility and on-off ratio) careful removal of the wrapping polymer chains seems crucial, for example, by washing or ultracentrifugation. More defined positioning of the SWNTs can be accomplished in directed self-assembly procedures. One possible strategy uses diblock copolymers containing a conjugated polymer block as dispersing moiety and a second block for directed self-assembly, for example, a DNA block for specific interaction with complementary DNA strands. Another strategy utilizes reactive side chains for controlled anchoring onto patterned surfaces (e.g., by interaction of thiol-terminated alkyl side chains with gold surfaces). A further promising application of purified SWNT dispersions is the field of organic (all-carbon) or hybrid solar cell devices.