Thin films of microporous polymer networks (MPNs) have been generated by electrochemical polymerization of a series of multifunctional carbazole-based monomers. The microporous films show high Brunauer-Emmett-Teller (BET) surface areas up to 1300 m2 g(-1) as directly measured by krypton sorption experiments. A correlation between the number of polymerizable carbazole units of the monomer and the resulting surface area is observed. Electrochemical sensing experiments with 1,3,5-trinitrobenzene as prototypical nitroaromatic analyte demonstrate an up to 180 times increased current response of MPN-modified glassy carbon electrodes in relation to the nonmodified electrode. The phenomenon probably involves intermolecular interactions between the electron-poor nitroaromatic analytes and the electron-rich, high surface area microporous deposits, with the electrochemical reduction at the MPN-modified electrodes being an adsorption-controlled process for low scan rates. We expect a high application potential of such MPN-modified electrodes for boosting the sensitivity of electrochemical sensor devices.

Four thiophene-based monomers have been synthesized by Stille-or Suzuki-type couplings followed by chemical or electrochemical polymerization into microporous polymer networks (MPNs) with high BET surface areas (S BET ). Similar S BET values of up to 2020 and 2135 m 2 g −1 have been determined for tetraphenylmethane-cored bulk MPN powders and thin films, respectively. Electrochemical polymerization in boron trifluoride diethyl etherate (BFEE)/dichloromethane (DCM) mixtures allows for the generation of MPN films with optimized porosity. Moreover, an interesting effect of boron trifluoride on the connectivity of the monomeric units during electropolymerization is observed for 3-thienyl-based monomers. Finally, the electrochemical reduction of 1,3,5trinitrobenzene at MPN-modified glassy carbon (GC) electrodes shows increased cathodic responses compared to nonmodified GC electrodes due to interaction between electron-deficient nitroaromatic analyte and electron-rich MPN film. The influence of the specific surface area of MPNs on the electrochemical response is also studied for this class of materials.

Novel conjugated polymers based on 3,6-carbazole repeat units were synthesized by nickel-catalyzed Yamamoto coupling under microwave heating. The resulting poly(3,6-carbazole)s contain tetraphenylethylene (TPE) units in their side chains. The resultant polymers show aggregation induced emission (AIE) behavior. Hereby, the photoluminescence (PL) intensity of PCzTPE0.5 in 90% water-THF is 35 times higher than that in pure THF, connected to the introduction of TPE side chains. The ability of polymer PCzTPE0.5 for explosive sensing was also studied. A maximum Stern-Volmer quenching constant of 1.26 Â 10 6 M À1 was observed for PL quenching of PCzTPE0.5 aggregates by trinitrobenzene (TNB). A solid state paper strip test based on PCzTPE0.5 and PCzTPE also demonstrates effective PL quenching towards both TNB vapor and solution.

We propose microporous networks (MPNs) of a light emitting spiro-carbazole based polymer (PSpCz) as luminescent sensor for nitro-aromatic compounds. The MPNs used in this study can be easily synthesized on arbitrarily sized/shaped substrates by simple and low-cost electrochemical deposition. The resulting MPN afford an extremely high specific surface area of 1300 m2/g, more than three orders of magnitude higher than that of the thin films of the respective monomer. We demonstrate, that the luminescence of PSpCz is selectively quenched by nitro-aromatic analytes, e.g. nitrobenzene, 2,4-DNT and TNT. In striking contrast to a control sample based on non-porous spiro-carbazole, which does not show any luminescence quenching upon exposure to TNT at levels of 3 ppm and below, the microporous PSpCz shows a clearly detectable response even at TNT concentrations as low as 5 ppb, clearly demonstrating the advantage of microporous films as luminescent sensors for traces of explosive analytes. This level states the vapor pressure of TNT at room temperature.

Chemically and electrochemically generated novel microporous polymer networks (MPNs) have been prepared from tetraphenylethene (TPE)-cored, multifunctional carbazole- or thiophene-based monomers for the fluorescence sensing of nitroaromatic analytes.

Electrochemical sensors appear as low-cost, rapid, easy to use, and in situ devices for determination of diverse analytes in a liquid solution. In that context, conducting polymers are much-explored sensor building materials because of their semiconductivity, structural versatility, multiple synthetic pathways, and stability in environmental conditions. In this state-of-the-art review, synthetic processes, morphological characterization, and nanostructure formation are analyzed for relevant literature about electrochemical sensors based on conducting polymers for the determination of molecules that (i) have a fundamental role in the human body function regulation, and (ii) are considered as water emergent pollutants. Special focus is put on the different types of micro- and nanostructures generated for the polymer itself or the combination with different materials in a composite, and how the rough morphology of the conducting polymers based electrochemical sensors affect their limit of detection. Polypyrroles, polyanilines, and polythiophenes appear as the most recurrent conducting polymers for the construction of electrochemical sensors. These conducting polymers are usually built starting from bifunctional precursor monomers resulting in linear and branched polymer structures; however, opportunities for sensitivity enhancement in electrochemical sensors have been recently reported by using conjugated microporous polymers synthesized from multifunctional monomers.

Electrochemical oxidative polymerization of rigid, multifunctional monomers allows for the synthesis of microporous thin films with high surface areas. Multifunctional, carbazole‐ and thiophene‐based rigid monomers have been utilized as rigid 3D building blocks (tectons) toward microporous polymer films with relatively smooth surface morphology. Within the last four years, several studies following this approach have been published that report interesting results on the application of these electrogenerated films in organic electronics, photoluminescence‐based or electrochemical chemodetectors, electrochemical supercapacitors, and light‐harvesting antennae for exciton pumping. In this work, the synthetic approaches for the electrochemical polymerization of multifunctional carbazole‐ and thiophene‐based tectons as well as resulting properties and application possibilities of the electrogenerated microporous polymer films are reviewed.

A new ultra low band gap (LBG) α,β-unsubstituted BODIPY-based conjugated polymer has been synthesized by conventional cross coupling polymerization techniques (Stille cross coupling) for the first time. The polymer exhibits a panchromatic absorption spectrum ranging from 300 nm to 1100 nm and an optical band gap (Eg opt ) of 1.15 eV, suitable for near infrared (NIR) organic photovoltaic applications as electron donor. Preliminary power conversion efficiency (PCE) of 1.1 % in polymer:[6,6]-phenyl-C71-butyric acid methyl ester (PC71BM) 1:3 weight ratio bulk heterojunction (BHJ) solar cells has been achieved, demonstrating very interesting and promising photovoltaic characteristics, such as good fill factor (FF) and open circuit voltage (Voc). These results showing that by the proper chemical design, new α,β-unsubstituted BODIPYbased NIR copolymers can be developed in the future with suitable energy levels matching those of PC71BM towards more efficient NIR organic photovoltaics (OPVs).