Controlled synthesis of ZnO nanoparticles from a Zn(II) coordination polymer: Structural characterization,optical properties and photocatalytic activity

A zinc coordination polymer derived from pyridine-2,6-dicarboxylate (PDC), {[Zn₂(PDC)₂]}_n, was successfully prepared via conventional, sonication and microwave-irradiation methods. The composition and characteristics of the obtained coordination polymers (CPs) were investigated by elemental analysis, TGA/DTA, X-ray diffraction and spectroscopic techniques. The so obtained CPs were heat-treated in the air at 600 °C for 2 h to produce ZnO of nanosized particles (NPs). It is of interest to note that the synthesis approach of the precursor greatly affects both the nanoparticle size and the structure of the resulting ZnO NPs. Moreover, the smallest particle size was associated with the sample derived from the ultrasonically prepared precursor. TEM analysis revealed that all samples have sphere-like morphologies. Structural analysis of the prepared ZnO samples was conducted and compared using Rietveld analysis of their PXRD patterns. Optical band gap calculations based on analysis of the UV–vis spectra of ZnO samples using Tauc's power law were achieved. The highest band gap of 3.63 eV was observed for ZnO sample obtained from the ultrasonically prepared precursor. Furthermore, the photocatalytic activity of ZnO NPs for the removal of Eosin Y color was monitored. The highest removal efficiency was recorded for ZnO originated from the ultrasonically synthesized precursor. Enhancement of removal efficiency that reached 98% was attained in only a period of 8 min. Its recycling test showed that it can be reused without structural changes over four cycling experiments.     

Divergent strategy for the synthesis of bottlebrush polymers via postpolymerization modification of macromonomer

A simple and divergent synthetic strategy of bottlebrush polymers (BBPs) is presented, consisting of postpolymerization modification of a macromonomer and grafting-through polymerization. Beginning with a single macromonomer, its direct modification could build a library of macromonomers with an identical chain length, thus guaranteeing the precision in the synthesis of BBPs. In this study, a newly designed norbornenyl-terminated poly(methyl acrylate) (NB-PMA) is proposed as a chemically robust template. Ti-mediated transesterification of NB-PMA successfully produces structurally diverse polyacrylates while maintaining the terminal norbornenyl group intact. All macromonomers obtained from transesterification possess a good grafting-through ring-opening metathesis polymerization reactivity, furnishing homo, random, and block BBPs in a controllable manner. Moreover, atomic force microscopy analysis supports the controlled side-chain length distribution in the resulting BBPs.     

Mechanistic Study of the Solvent-Dependent Formation of Extended and Stacked Supramolecular Polymers Composed of Bis(imidazolylporphyrinatozinc) Molecules

Bis(imidazolylporphyrinatozinc) molecules linked through a 1,3-butadiynylene moiety respond to the solvents they are dissolved in to afford exclusively extended (E) or stacked (S) supramolecular polymers. This system is expected to be a solvation/desolvation indicator. However, the principles underlying the solvent-dependent formation of the two types of polymers and the mechanism of the transformation between them are unclear. The formation of the polymers is considered to depend on the two types of complementary coordination bonds that can be formed and the π–π interactions between the porphyrins. In this study, the contributions and solvent dependence of both the coordination bonds and the π–π interactions have been investigated. The results clearly indicate that the coordination bonds are weakly or little solvent-dependent, and that the π–π interactions function effectively only in the inner porphyrins of the S-polymer and are strongly solvent-dependent. Thermodynamic analysis revealed that the formation of the E- or S-polymer in solution is determined by the total energies and the type of solvent used. The transformation of the E- to S-polymer was investigated by gel permeation chromatography. The kinetics of the transformation were also determined. The role of the terminal imidazolylporphyrinatozinc moieties was also investigated: The results indicate that the transformation from the E- to S-polymer occurs by an exchange mechanism between the polymers, induced by attack of terminal free imidazolyl groups on a polymer to zinc porphyrins on other polymers.     

Norbornene derivatives from a metal‐free,strain‐promoted cycloaddition reaction: New building blocks for ring‐opening metathesis polymerization reactions

The preparation of new ring opening metathesis polymerization (ROMP) monomers using a 1,3‐dipolar cycloaddition between aryl azides and norbornadiene is described. Various norbornenetriazolines, obtained through a solvent‐and catalyst‐free reaction, can subsequently be incorporated into polymer backbones through ROMP reactions. Furthermore, thermal decomposition of the triazoline moiety can allow for further polymer functionalization. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 2357–2362     

Amphiphilic thermoset elastomers from metal‐free,click crosslinking of PEG‐grafted silicone surfactants

The hydrophobicity of silicone elastomers can compromise their utility in some biomaterials applications. Few effective processes exist to introduce hydrophilic groups onto a polysiloxane backbone and subsequently crosslink the material into elastomers. This problem can be overcome through the utilization of metal‐free click reactions between azidoalkylsilicones and alkynyl‐modified silicones and/or PEGs to both functionalize and crosslink silicone elastomers. Alkynyl‐functional PEG was clicked onto a fraction of the available azido groups of a functional polysiloxane, yielding azido reactive PDMS‐g‐PEG rake surfactants. The reactive polymers were then used to crosslink alkynyl‐terminated PDMS of different molecular weights. Using simple starting materials, this generic yet versatile method permits the preparation and characterization of a library of amphiphilic thermoset elastomers that vary in their composition, crosslink density, elasticity, hydrogel formation, and wettability. An appropriate balance of PEG length and crosslink density leads to a permanently highly wettable silicone elastomer that demonstrated very low levels of protein adsorption. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 1082–1093     

Study of spatial inhomogeneity in inverted all‐polymer solar cells: Effect of solvent and annealing

The efficiency optimization of bulk heterojunction solar cells requires the control of the local active materials arrangement in order to obtain the best compromise between efficient charge generation and charge collection. Here, we investigate the large scale (10–100 μm) inhomogeneity of the photoluminescence (PL) and the external quantum efficiency (EQE) in inverted all‐polymer solar cells (APSC) with regioregular poly(3‐hexylthiophene) (P3HT):poly(9,9‐dioctylfluorene‐co‐benzothiadiazole) (F8BT) active blends. The morphology and the local active polymer mixing are changed by depositing the active layer from four different solvents and by thermal annealing. The simultaneous PL and EQE mapping allowed us to inspect the effects of local irregularities of active layer thickness, polymer mixing, polymer aggregation on the charge generation and collection efficiencies. In particular, we show that the increase of the solvent boiling point affects the EQE non‐uniformity due to thickness fluctuations, the density non‐uniformity of rrP3HT aggregate phase, and the blend components clustering. The thermal annealing leads to a general improvement of EQE and to an F8BT clustering in all the samples with locally decrease of the EQE. We estimate that the film uniformity optimization can lead to a total EQE improvement between 2.7 and 6.3 times. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 804–813     

Synthesis and liquid crystalline behavior of bulky poly(methacrylamide)s

N‐(Bis(4‐(2‐ethylhexyloxy)phenyl)(phenyl)‐methyl)methacrylamide was synthesized and polymerized via reversible addition‐fragmentation chain‐transfer (RAFT) polymerization. The chain‐transfer agent (4‐cyano‐4‐(phenylcarbonothioylthio) pentanoic acid (CPADB)), combined with a chiral additive, and a radical initiator yielded polymers with dispersities between 1.2 and 1.4. At low concentrations, the polymers are soluble in hexanes and chloroform while at higher concentrations they swell in these solvents. Characterization of the polymers by wide‐angle X‐ray scattering (WAXS) revealed an interplanar distance of 19.0 Å. The WAXS data combined with polarized optical microscopy support a lamellar crystallization and lyotropic liquid crystalline behavior in hexanes and chloroform. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 2563–2568     

Solubility and Crystallizability: Facile Access to Functionalized π‐Conjugated Compounds with Chlorendylimide Protecting Groups

Functional π‐conjugated molecules are relevant for the preparation of new organic electronic materials with improved performance. However, their synthesis is often rendered difficult by their inherently low solubility, and the permanent attachment of solubilizing groups may change the properties of the material. Here, we introduced the chlorendylimidyl moiety as a new temporary protecting group for the straightforward large‐scale synthesis of protected quarter‐, sexi‐, octathiophene, and perylene bisimide diamine and dicarboxylic acid derivatives. The obtained chlorendylimides and chlorendylimidyl active esters were highly soluble in organic solvents, and optical spectroscopy confirmed the low tendency of the compounds to aggregate in solution. At the same time, they could be conveniently purified by recrystallization or precipitation. Single‐crystal X‐ray structures obtained for most compounds showed supramolecular motifs highlighting the role of the rigid, polychlorinated chlorendyl moieties in their crystallization. The obtained protected diamine and dicarboxylic acid derivatives were easily deprotected and converted into various amide‐substituted oligothiophenes and perylene bisimides that are of interest as new functional materials for organic electronic thin film or nanowire devices.     

Effect of branched alkyl side chains on the performance of thin‐film transistors and photovoltaic cells fabricated with isoindigo‐based conjugated polymers

New isoindigo and di(thienyl)ethylene‐containing π‐extended conjugated polymers with different branched side chains were synthesized to investigate their physical properties and device performance in thin‐film transistors and photovoltaic cells. 11‐Butyltricosane (S3) and 11‐heptyltricosane (S6) groups were used as side‐chain moieties tethered to isoindigo units. The linking groups between the polymer backbone and bifurcation point in the branched side chain differ in the two polymers (i.e., PIDTE‐S3 and PIDTE‐S6 ). The polymers bearing S6 side chains showed much better charge transport behavior than those with S3 side chains. Thermally annealed PIDTE‐S6 film exhibited an outstanding hole mobility of 4.07 cm² V^?1 s^?1 under ambient conditions. Furthermore, bulk heterojunction organic photovoltaic cells made from a blend film of PIDTE‐S3 and (6,6)‐phenyl C61‐butyric acid methyl ester demonstrated promising device performance with a power conversion efficiency in the range of 4.9–5.0%. © 2015 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 2015 , 53, 1226–1234